Rubber composition and articles therefrom both comprising mercapto-functional silane

ABSTRACT

The disclosure herein relates to organofunctional silanes and mixtures of organofunctional silanes possessing mercaptan and hydrocarbyl and/or heterocarbyl functionality. These silanes reduce or eliminate the generation of volatile organic compounds (VOC&#39;s) during use, aid in the processing of filled elastomeric materials and enhance the end-use properties of the filled elastomer. The present disclosure relates to a rubber composition and article comprising these silanes.

FIELD OF THE INVENTION

The present disclosure relates to a rubber composition and articlestherefrom both comprising organofunctional silanes and also relates to arubber composition and articles therefrom both comprising mixtures oforganofunctional silanes. The disclosure relates to a rubber compositionand articles therefrom both comprising these silanes.

DESCRIPTION OF THE RELATED ART

Mercaptosilanes and their use as coupling agents in filled elatomers areknown in the art. However, these silanes are very reactive with thefillers and organic polymers and are difficult to use in preparingfilled elastomers. When these silanes are used at levels necessary toachieve optimum coupling of the filler to the polymer, the uncuredfilled elastomer has short scorch times and poorly dispersed fillers.Long scorch times are necessary for mixing of the filler and otheringredients with the polymer, extrusion of the uncured elastomer andfabrication of articles without premature crosslinking or formation ofhigh viscosity compounds. Good dispersion of the filler is required toachieve end-use properties, such as weatherability, wear,tear-resistance and so on. These silanes are also derived from monolfunctional alcohols that generate volatile organic compound (VOC)emissions during fabrication and use.

Glycol derivatives of organosilanes are known in the art. However, thesesilane derivatives suffer from a tendency to yield bridged structures infavor of cyclic structures exclusively or primarily, leading to highviscosities and gellation, which limits their usefulness in elastomermanufacture.

In addition to the need to reduce VOC's during the preparation ofinorganic filled elastomers, there is also a need to improve thedispersion of the inorganic fillers in organic polymers whilemaintaining processability of the elastomeric compositions. Betterdispersion improves the performance of cured articles, such as tires, byreducing rolling resistance, heat build-up and wear.

Recently, the present inventors addressed in U.S. patent applicationSer. Nos. 11/358,550; 11/358,818; 11/358,369; 11/358,861 all filed onFeb. 21, 2006, the scorch, VOC emissions and coupling performance offilled elastomers using organofunctional silanes or mixtures oforganofunctionals silanes that contain both blocked and free mercaptangroups. In addition, the present inventors addressed in U.S. patentapplication Ser. No. 11/104,103, filed on Apr. 12, 2005, the VOCemissions using organofunctional silanes containing dialkoxysilylgroups.

SUMMARY OF THE INVENTION

In one embodiment, the present disclosure is directed to a rubbercomposition comprising:

(a) at least one rubber component, (b) at least one particulate fillerand (c) at least one mercaptofunctional silane composition comprising atleast one organofunctional silane selected from the group consisting of:

-   -   (i) mercaptosilane possessing at least one hydroxyalkoxysilyl        group and/or a cyclic dialkoxysilyl group,    -   (ii) hydrocarbyl and/or heterocarbyl silane possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,    -   (iii) mercaptosilane dimer in which the silicon atoms of the        mercaptosilane units are bonded to each other through a bridging        dialkoxy group, each silane unit optionally possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,    -   (iv) hydrocarbyl and/or heterocarbyl silane dimer in which the        silicon atoms of the hydrocarbyl and/or heterocarbyl silane        units are bonded to each other through a bridging dialkoxy        group, each silane unit optionally possessing at least one        hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,    -   (v) silane dimer possessing a mercaptosilane unit the silicon        atom of which is bonded to the silicon atom of a hydrocarbyl        and/or heterocarbyl silane unit through a bridging dialkoxy        group, each silane unit optionally possessing at least one        hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,    -   (vi) mercaptosilane oligomer in which the silicon atoms of        adjacent mercaptosilane units are bonded to each other through a        bridging dialkoxy group, the terminal mercaptosilane units        possessing at least one hydroxyalkoxysilyl group and/or a cyclic        dialkoxysilyl group,    -   (vii) hydrocarbyl and/or heterocarbyl silane oligomer in which        the silicon atoms of adjacent hydrocarbyl and/or heterocarbyl        silane units are bonded to each other through a bridging        dialkoxy group, the terminal mercaptosilane units possessing at        least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group, and    -   (viii) silane oligomer possessing at least one mercaptosilane        unit and at least one hydrocarbyl and/or heterocarbyl silane        unit, the silicon atoms of adjacent silane units being bonded to        each other through a bridging dialkoxy group, the terminal        silane units possessing at least one hydroxyalkoxysilyl group        and/or a cyclic dialkoxysilyl group, with the provisio that,        where the composition contains one or more of (i), (iii) and        (vi), the composition additionally contains one or more of (ii),        (iv), (v), (vii) and (viii), and where the composition contains        one or more of (ii), (iv) and (vii), the composition        additionally contains one or more of (i), (iii), (v), (vi) and        (viii).

In one other embodiment as will be appreciated from the foregoing,compositions made by the process described herein can include one ormore silane dimers and/or oligomers in which adjacent silane units arebonded to each other through bridged dialkoxysilane structures derivedfrom polyhydroxy-containing compounds, e.g., diols (glycols), triols,tetrols, etc., all of which are low volatile organic compounds (VOCs)relative to simple monohydroxy-containing compounds such as methanol andethanol which are released by known organosilanes.

In another embodiment, it will also be appreciated that all of thecompositions made by the process within the scope of the inventioncontain both mercapto, and hydrocarbyl and/or heterocarbylfunctionalities, either present in the same silane or in mixtures ofindividual silanes. While it is known that silanes possessingexclusively mercaptan functionality are prone to scorch, it has come asa surprise that the compositions of this invention which possess bothmercaptan, and hydrocarbyl and/or heterocarbyl functionalities, possesslong scorch times, e.g., approaching those of silanes possessingexclusively blocked mercaptan or polysulfide groups, but withsignificantly better performance than the latter.

DETAILED DESCRIPTION OF THE INVENTION

The expression “organofunctional silane” as used herein shall beunderstood to mean a non-polymeric, dimeric or oligomeric silanepossessing mercaptan and hydrocarbyl and/or heterocarbyl functionalityand at least one hydroxyalkoxysilyl and/or cyclic dialkoxysilyl group,and, in the case of the dimeric and oligomeric organofunctional silanes,possessing dialkoxy bridging groups linking adjacent silane units.

In one embodiment herein, it will be understood that all ranges hereininclude all subranges therebetween. In another specific embodimentherein, it will be understood that all listings of members of a groupcan further comprise combinations of any two or more of the members ofsaid group. In another embodiment herein, it will be understood thatU.S. Patent Applications, with the same inventors as herein, and filedon same date as the subject application, and entitled:Mercapto-functional Silane; Process for Making Mercapto-functionalSilane; and A Free Flowing Filler Composition ComprisingMercapto-functional Silane are all incorporated by reference herein intheir entireties.

In another embodiment herein there is provided a process for thepreparation of a mercaptofunctional silane comprising:

a) reacting at least one organofunctional silane selected from the groupconsisting of:

G′-(SiX₃)_(s)  (1)

[G³-(YG²-)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

and at least one mercapto functional silane of general formula:

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein:

each occurrence of Y is independently selected from a polyvalent species(-Q)_(a)[C(=E)]_(b)(A-)_(c), wherein the atom (E) is attached to anunsaturated carbon atom;

each occurrence of G¹ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G¹ can have from 1 to about30 carbon atoms;

each occurrence of G² is independently selected from the groupconsisting of divalent or polyvalent group derived by substitution ofalkyl, alkenyl, aryl, or aralkyl wherein G² can have from 1 to 30 carbonatoms;

each occurrence of G³ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G³ can have from 1 to about30 carbon atoms, with the proviso that if G³ is monovalent, G³ can behydrogen;

each occurrence of X is independently selected from the group consistingof —Cl, —Br, RO—, RC(═O)O—, R₂C═NO—, R₂NO—, R₂N—, —R, wherein each R isindependently selected from the group consisting of hydrogen, straight,cyclic or branched alkyl that can or can not contain unsaturation,alkenyl groups, aryl groups, and aralkyl groups, wherein each R, otherthan hydrogen, contains from 1 to 18 carbon atoms;

each occurrence of Q is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when Q issulfur, b is 0;

each occurrence of A is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when A issulfur, b is 0;

each occurrence of E is independently selected from the group consistingof oxygen, sulfur, and (—NR—);

each occurrence of the subscripts, a, b, c, j, k, r, and s areindependently integers given by a is 0 or 1; b is 0 or 1; c is 0 or 1; jis of from about 1 to about 3; k is of from about 0 to about 15; r is offrom about 1 to about 3; and s is of from about 1 to about 3, and withthe proviso that each of the above structures (1), (2) and (3) containsat least one hydrolysable X group;

b) with one or more polyhydroxy-containing compounds of the generalformula:

G⁴(OH)_(d)  (6)

wherein G⁴ is a hydrocarbon group of from 1 to about 15 carbon atoms ora heterocarbyl group of from 4 to about 15 carbon atoms containing oneor more etheric oxygen atoms and d is an integer of from about 2 toabout 8, under tranesterification reaction conditions.

In one embodiment herein, organofunctional silanes (i)-(viii) describedherein, and their mixtures, can be obtained, inter alia, from one ormore silane reactants of the general formulae:

G¹-(SiX₃)_(s)  (1)

[G³-(YG²-)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein:

each occurrence of Y is independently selected from a polyvalent species(-Q)_(a)[C(=E)]_(b)(A-)_(c), wherein the atom (E) is attached to anunsaturated carbon atom;

each occurrence of G¹ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G¹ can have from 1 to about30 carbon atoms;

each occurrence of G² is independently selected from the groupconsisting of divalent or polyvalent group derived by substitution ofalkyl, alkenyl, aryl, or aralkyl wherein G² can have from 1 to 30 carbonatoms;

each occurrence of G³ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G³ can have from 1 to about30 carbon atoms, with the proviso that if G³ is monovalent, G³ can behydrogen;

each occurrence of X is independently selected from the group consistingof —Cl, —Br, RO—, RC(═O)O—, R₂C═NO—, R₂NO—, R₂N—, —R, wherein each R isindependently selected from the group consisting of hydrogen, straight,cyclic or branched alkyl that can or can not contain unsaturation,alkenyl groups, aryl groups, and aralkyl groups, wherein each R, otherthan hydrogen, contains from 1 to 18 carbon atoms;

each occurrence of Q is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when Q issulfur, b is 0;

each occurrence of A is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when A issulfur, b is 0;

each occurrence of E is independently selected from the group consistingof oxygen, sulfur, and (—NR—);

each occurrence of the subscripts, a, b, c, j, k, r, and s areindependently integers given by a is 0 or 1 and more specifically 1; bis 0 or 1 and more specifically 0; c is 0 or 1 and more specifically 0;j is specifically of from about 1 to about 3, more specifically fromabout 1 to about 2 and most specifically 1; k is specifically of fromabout 0 to about 15, more specifically from about 0 to about 5, and mostspecifically from about 0 to about 2; r is specifically of from about 1to about 3, and more specifically about 1; and s is specifically of fromabout 1 to about 3, and more specifically about 1, and with the provisothat each of the above structures (1), (2) and (3) contains at least onehydrolysable X group.

In one particular embodiment of the invention, the silane reactants aretrialkoxysilanes represented by at least one of the general Formulae (4)and (5):

(RO)₃SiG¹  (4)

(RO)₃SiG²SH  (5)

wherein each R independently has one of the aforestated meanings and,advantageously, is a methyl, ethyl, propyl, isopropyl, n-butyl, orsec-butyl group; G² is an alkylene group of from 1 to about 12 carbonatoms; and, G¹ is an alkyl group of from 3 to about 18 carbon atoms.

In a specific embodiment herein, mixtures of silane monomers ((1), (2)and/or (3)) can be used, such as the non-limiting examples of, two ormore mercaptotrialkoxysilanes of Formula (5), two or morehydrocarbyltrialkoxysilanes of Formula (4) and mixtures of one or moremercaptotrialkoxysilanes of Formula (5) and one or morehydrocarbyltrialkoxysilanes of Formula (4) with R, G¹ and G² in thesesilanes being defined as in silanes of Formulae (1) and (3).

In one embodiment herein, in a silane dimer or oligomer, each silaneunit of the dimer or oligomer is bonded to an adjacent silane unitthrough a bridging group resulting from the reaction of the selectedsilane monomer(s) with one or more polyhydroxy-containing compounds ofthe general formula:

G⁴(OH)_(d)  (6)

wherein G⁴ is a hydrocarbon group of from 1 to about 15 carbon atoms ora heterocarbyl group of from 4 to about 15 carbon atoms containing oneor more etheric oxygen atoms and d is an integer of specifically fromabout 2 to about 8, more specifically of from about 2 to about 4 andmost specifically about 2.

In one embodiment herein, polyhydroxy-containing compound of Formula (6)is a diol (glycol) of at least one of the general Formulae (7) and (8):

HO(R⁰CR⁰)_(f)OH  (7)

HO(CR⁰ ₂CR⁰ ₂O)_(e)H  (8)

wherein R⁰ is independently given by one of the members listed above forR, f is 2 to about 15 and e is 2 to about 7. In one embodiment, somerepresentative non-limiting examples of such diols are HOCH₂CH₂OH,HOCH₂CH₂CH₂OH, HOCH₂CH₂CH₂CH₂OH, HOCH₂CH(CH₃)CH₂OH,(CH₃)₂C(OH)CH₂CH(OH)CH₃, CH₃CH(OH)CH₂CH₂OH, a diol possessing an ethericoxygen-containing group such as HOCH₂CH₂OCH₂CH₂OH, HOCH₂CH₂CH₂OCH₂CH₂CH₂OH, HOCH₂CH(CH₃)OCH₂CH(CH₃)OH and a diol possessing a polyetherbackbone such as the non-limiting example of HOCH₂CH₂OCH₂CH₂OCH₂CH₂OH, adiol of Formula (8) in which R⁰ is hydrogen or methyl and e is 3 toabout 7.

In another embodiment herein, the polyhydroxy-containing compound ofFormula (6) is a diol of Formula (7).

In another embodiment herein, polyhydroxy-containing compound of Formula(6) possesses higher hydroxyl functionality, and is such as thenon-limiting examples selected from the group consisting of, a triol ortetrol, of the general Formula (9):

G⁴(OH)_(d)  (9)

wherein G⁴ is a is a substituted hydrocarbon group from 2 to about 15carbon atoms or a substituted heterocarbon from 4 to about 15 carbonatoms and contains one or more etheric oxygen atoms; and d is an integerof from 3 to about 8. In one embodiment some non-limiting examples ofhigher hydroxyl functionality compounds (9) include glycerol,trimethylolethane, trimethylolpropane, 1,2,4-butanetriol,1,2,6-hexanetriol, pentaerythritol, dipentaerythritol,tripentaerythritol, mannitol, galacticol, sorbitol, and combinationsthereof.

In another embodiment, mixtures of polyhydroxy-containing compounds ofFormula (6) can also be used herein.

In one embodiment herein, organofuntional silanes (i)-(viii) andmixtures thereof can be prepared by the process which comprises reactingat least one silane of one or more of general Formulae (1), (2), and/or(3) as herein:

G¹-(SiX₃)_(s)  (1)

[G³-(YG²-)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

(HS)_(r)-G²-(SiX₃)_(s)  (3)

with at least one polyhydroxy-containing compound of the general Formula(6):

G⁴(OH)_(d)  (6)

wherein each occurrence of G¹, G², G³, G⁴, R, Y, X, a, b, c, d, j, k, r,and s are defined as herein and with the proviso that at least one ofthe X is a hydrolyzable group, each of the aforesaid having the meaningspreviously stated, under transesterification reaction conditions.

In a first embodiment of the foregoing process, at least one hydrocarbylof Formula (1) and/or heterocarbylsilane of Formula (2) istransesterified with at least one polyhydroxy-containing compound ofFormula (6), optionally, in the presences of catalyst, e.g.,transesterification catalyst, to provide one or more organofunctionalhydrocarbylsilane and/or heterocarbylsilanes (ii), (iv) and (vii), andmercaptosilane of Formula (3) is transesterified with at least onepolyhydroxy-containing compound of Formula (6), optionally, in thepresences of catalyst, e.g., transesterification catalyst, to provideone or more part or all of the mercaptosilane(s) providing one or moreorganofunctional silanes (i), (iii), and (vi), any of which can be inadmixture with one or more of (ii), (iv), and (vii).

In a second embodiment of the foregoing process, organofunctionalsilanes (i), (iii) and (vi) can further transesterify withorganofunctional silanes (ii), (iv) and (vii) to form (v) or (viii), anyof which can be in admixture with one or more of (i), (ii), (iii), (iv),(vi) and (vii). In one embodiment the mercaptofunctional silanecomposition described herein comprises at least one mixture selectedfrom the group consisting of (i) and one or more of (ii), (iv), (v),(vii) and (viii); (ii) and one or more of (iii), (v), (vi) and (viii);(iii) and one or more of (v), (vii) and (viii); (iv) and one or more of(v), (vi) and (viii); (v) and either or both of (vi) and (vii); (vi) andeither or both of (vii) and (viii); and, (vii) and (viii). In anotherembodiment there is provided a mercaptofunctional silane composition asdescribed herein wherein (i) possesses one or two hydroxyalkoxysilylgroups and/or a cyclic dialkoxysilyl group; (ii) possesses one or twohydroxyalkoxysilyl groups and/or a cyclic dialkoxysilyl group; eachsilane unit of (iii) independently possesses one or twohydroxyalkoxysilyl groups and/or a cyclic dialkoxysilyl group; eachsilane unit of (iv) independently possesses one or twohydroxyalkoxysilyl groups and/or a cyclic dialkoxysilyl group; eachsilane unit of (v) independently possesses one or two hydroxyalkoxysilylgroups and/or a cyclic dialkoxysilyl group; (vi) possesses from 3 toabout 20 mercaptosilane units, the terminal mercaptosilane unitsindependently possessing one or two hydroxyalkoxysilyl groups and/or acyclic dialkoxysilyl group; (vii) possesses from 3 to about 20hydrocarbylsilane and/or heterocarbylsilane units, the terminalhydrocarbylsilane or heterocarbylsilane units independently possessingone or two hydroxyalkoxysilyl groups and/or a cyclic dialkoxysilylgroup; and, (viii) possesses from 3 to about 40 silane units of whichfrom 1 to about 20 are mercaptosilane units and from 1 to about 20 arehydrocarbylsilane and/or heterocarbylsilane units, the terminal silaneunits independently possessing one or two hydroxyalkoxysilyl groupsand/or a cyclic dialkoxysilyl group. In yet another embodiment there isprovided a mercaptofunctional silane composition as described hereinwherein (i) possesses one or two hydroxyalkoxysilyl groups and/or acyclic dialkoxysilyl group; (ii) possesses one or two hydroxyalkoxysilylgroups and/or a cyclic dialkoxysilyl group; each silane unit of (iii)independently possesses one or two hydroxyalkoxysilyl groups and/or acyclic dialkoxysilyl group; each silane unit of (iv) independentlypossesses one or two hydroxyalkoxysilyl groups and/or a cyclicdialkoxysilyl group; each silane unit of (v) independently possesses oneor two hydroxyalkoxysilyl groups and/or a cyclic dialkoxysilyl group;(vi) possesses from 3 to about 10 mercaptosilane units, the terminalmercaptosilane units independently possessing one or twohydroxyalkoxysilyl groups and/or a cyclic dialkoxysilyl group; (vii)possesses from 3 to about 10 hydrocarbylsilane and/or heterocarbylsilaneunits, the terminal hydrocarbylsilane or heterocarbylsilane unitsindependently possessing one or two hydroxyalkoxysilyl groups and/or acyclic dialkoxysilyl group; and, (viii) possesses from 3 to about 20silane units of which from 1 to about 10 are mercaptosilane units andfrom 1 to about 10 are hydrocarbylsilane and/or heterocarbylsilaneunits, the terminal silane units independently possessing one or twohydroxyalkoxysilyl groups and/or a cyclic dialkoxysilyl group. Inanother embodiment herein there is provided a mercaptofunctional silanecomposition as described herein wherein in each mixture, the ratio ofmercaptan to hydrocarbyl group and/or heterocarbyl group ranges fromabout 20:1 to about 0.05:1.

In one application of this first embodiment of the general preparativeprocess herein, at least one hydrocarbyltrialkoxysilane of Formula (4)is transesterified with at least one diol of Formula (7) or (8),optionally, in the presence of a transesterification catalyst such asthe non-limiting example of para-toluenesulfonic acid, to provideorganofunctional silane (vii), i.e. the non-limiting example ofhydrocarbylsilane oligomer, mercaptotrialkoxysilane of Formula (5) istransesterified with at least one diol of Formula (7) or (8),optionally, in the presence of a transesterification catalyst such asthe non-limiting example of para-toluenesulfonic acid, to provideorganofunctional silane (vi), i.e. the non-limiting example ofmercaptosilane oligomer, which is then mixed with organofunctionalsilane (vii) and subjected to further transesterification, optionally,in the presence of transesterification catalyst, to yield one or moreorganofunctional silanes (viii), i.e. the non-limiting example of silaneoligomer containing one or more mercaptosilanes and one or morehydrocarbylsilanes, alone or in combination with one or more otherorganofunctional silanes (i)-(v).

In a third embodiment of the general preparative procedure herein, atleast one mercaptosilane of Formula (3) in admixture with at least onehydrocarbylsilane of Formula (1) and/or heterocarbylsilane of Formula(2) are transesterified with at least one polyhydroxy-containingcompound of Formula (6), optionally, in the presence transesterificationcatalyst, to provide, inter alia, one or more organofunctional silanes(v) and/or (viii), and/or other mixtures of organofunctional silanes,e.g. the non-limiting examples of a mixture of silanes (i) and (ii); (i)and (v); (i), (ii) and (v); (ii) and (viii); (ii), (v) and (viii); (i),(ii), (v) and (viii), and the like.

In one application of the foregoing third embodiment of the generalpreparative process, at least one mercaptotrialkoxysilane of Formula (5)and at least one heterocarbyltrialkoxysilane of Formula (4) aretransesterified together with at least one diol of Formula (7),optionally, in the presence of transesterification catalyst, to provideone or more silanes (v) and/or (viii).

In a fourth embodiment of the general preparative process, at least onemercaptosilane of Formula (3) is transesterified with at least onepolyhydroxy-containing compound of Formula (6), optionally, in thepresence of transesterification catalyst, to provide at least one dimer(iii) and/or oligomer (vi), or mercaptosilane (i) alone or in admixturewith dimer (iii) and/or oligomer (iv).

In one application of the foregoing fourth embodiment of the generalpreparative process, at least one mercaptotrialkoxysilane of Formula (5)is transesterified with at least one diol of Formula (7), optionally, inthe presence of transesterification catalyst, to provide mercaptosilanedimer (iii) and/or oligomer (vi).

In one embodiment, it is also to be understood herein that part or allof the esterification product(s) obtained from one of theafore-described process embodiments can be combined with part or all ofthe product(s) obtained from one of the other process embodiments. Thus,in one non-limiting example, hydrocarbylsilane and/or heterocarbylsilanedimer (iv) and/or hydrocarbylsilane and/or heterocarbylsilane oligomer(vii) resulting from the first preparative procedure can be admixed withmercaptosilane dimer (iii) and/or mercaptosilane oligomer (vi) toprovide a mixture of organofunctional silanes possessing both mercaptanand hydrocarbyl and/or heterocarbyl functionalities. In anotherembodiment, in a similar manner, simple mixing of the esterifiedproduct(s) of one particular embodiment of the general preparativeprocess can be admixed with the esterified product(s) of anotherembodiment of the general preparative process to provide still othercompositions within the scope of the invention possessing both mercaptanand hydrocarbyl and/or heterocarbyl functionality.

In one embodiment, reaction conditions for the process of preparingorganofunctional silanes (i)-(viii) and their mixtures include molarratios of silane(s), determined by adding the individual molarcontribution of silanes of Formulae (1), (2) and (3), andpolyhydroxy-containing compound(s) of Formula (6) of specifically fromabout 0.1 to about 3 moles of compound of Formula (6) per mole of silylgroup, more specifically from about 0.5 to about 2 moles of compound ofFormula (6) per mole of silyl group, and most specifically from about 1to about 1.5 moles of of Formula (6) per mole of silyl group, determinedby adding the individual contribution of silanes of Formulae (1), (2)and (3), a temperature of from about 0° C. to about 150° C., a pressureof from about 0.1 to about 2,000 mmHg, and in the optional presence ofcatalyst, solvent, and the like.

In a specific embodiment herein, an mercaptofunctional and cyclic and/orbridging dialkoxy silane composition is provided comprising at least onesilane selected from the group consisting of:

[G¹-(SiX^(α) _(u)Z^(β) _(v)Z^(θ) _(w))_(s)]_(m)[(HS)_(r)-G²-(SiX^(α)_(u)Z^(β) _(v)Z^(β) _(w))_(s)]_(n)  (10)

and

[[G³-(YG²)_(k)Y]_(j)G²-(SiX^(α) _(u)Z^(β) _(v)Z^(θ)_(w))_(s)]_(m)[(HS)_(r)-G²-(SiX^(α) _(u)Z^(β) _(v)Z^(θ)_(w))_(s)]_(n)  (11)

wherein:

each occurrence of Y is independently selected from a polyvalent species(-Q)_(a)[C(=E)]_(b)(A-)_(c), wherein the atom (E) is attached to anunsaturated carbon atom;

each occurrence of G¹ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G¹ can have from 1 to about30 carbon atoms;

each occurrence of G² is independently selected from the groupconsisting of divalent or polyvalent group derived by substitution ofalkyl, alkenyl, aryl, or aralkyl wherein G² can have from 1 to 30 carbonatoms;

each occurrence of G³ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G³ can have from 1 to about30 carbon atoms, with the proviso that if G³ is monovalent, G can behydrogen;

each occurrence of X^(α) is independently selected from the groupconsisting of —Cl, —Br, RO—, RC(═O)O—, R₂C═NO—, R₂NO—, R₂N—, —R,(HO)_(d-1)G⁴O —, HO(CR⁰ ₂)_(f)O—, and HO(CR⁰ ₂CR⁰ ₂O)_(e)—, wherein eachR is independently selected from the group consisting of hydrogen,straight, cyclic or branched alkyl that can or can not containunsaturation, alkenyl groups, aryl groups, and aralkyl groups, whereineach R other than hydrogen, contains from 1 to 18 carbon atoms, G⁴ isindependently a substituted hydrocarbon group from 2 to about 15 carbonatoms or a substituted heterocarbon group from about 4 to about 15carbon atoms and contains one or more etheric oxygen atoms, R⁰ isindependently given by one of the members listed for R, f is 2 to about15 and e is 2 to about 7;

each occurrence of Q is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when Q issulfur, b is 0;

each occurrence of A is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when A issulfur, b is 0;

each occurrence of E is independently selected from the group consistingof oxygen, sulfur, and (—NR—);

each occurrence of Z^(β), which forms a bridging structure between twosilicon atoms, is independently selected from the group consisting of,[—OG⁴(OH)_(d-2)O—]_(0.5), [—O(CR⁰ ₂CR⁰ ₂O)_(e)—]_(0.5) and[—O(R⁰CR⁰)_(f)O—]_(0.5), wherein each occurrence of R⁰ is independentlygiven by one of the members listed above for R; and, each occurrence ofG⁴ is independently selected form the group consisting of a substitutedhydrocarbon group from 2 to 15 carbon atoms or a substituted hetercarbonfrom 4 to 15 carbon atoms and contain one or more etheric oxygen atoms;

each occurrence of Z^(θ), which forms a cyclic structure with a siliconatom, is independently given by —OG⁴(OH)_(d-2)O—, —O(CR⁰ ₂CR⁰ ₂O)_(e)—and —O(R⁰CR⁰)_(f)O— wherein

each occurrence of R⁰ is independently given by one of the memberslisted above for R; each occurrence of the subscripts, a, b, c, d, e, f,j, k, m, n, r, s, u, v and w are integers independently given by a isspecifically 0 or 1, and more specifically 1; b is specifically 0 or 1,and more specifically 0; c is specifically 0 or 1, and more specifically0; d is specifically from about 2 to about 8, more specifically fromabout 2 to about 4 and most specifically about 2; e is specifically fromabout 2 to about 7, more specifically from about 2 to about 4 and mostspecifically about 2; f is specifically from about 2 to about 15, morespecifically from about 2 to about 4 and most specifically about 3; j isspecifically from 1 to about 3, more specifically 1 to about 2 and mostspecifically 1; k is specifically from 0 to about 15, more specificallyfrom about 0 to about 5, and most specifically from about 0 to about 2;m is specifically from about 1 to about 20, more specifically from about1 to about 5 and most specifically from about 2 to about 4; n isspecifically from about 1 to about 20, more specifically from about 1 toabout 5 and most specifically from about 2 to about 4; r is specificallyfrom 1 to about 3, and more specifically about 1; and s is specificallyfrom 1 to about 3, and more specifically about 1; u is specifically from0 to 3, more specifically from about 0 to about 2, and most specificallyfrom about 0 to about 1; v is specifically from 0 to 3, morespecifically from about 0 to about 2, and most specifically from about 0to about 1; w is specifically from 0 to about 1, and more specificallyabout 1; with the proviso that u+v+2w=3; and with the proviso that theeach of the above structures (10) and/or (11) contains at least onehydrolysable group, Z^(β) or Z^(θ).

In one embodiment it is understood that the structure,[—OG⁴(OH)_(d-2)(OH)_(d-2)]_(0.5) can further react with a third or moresilyl groups to form bridging trialkoxysilyl, tetraalkoxysilyl groupsand so on, and are represented by [—OG⁴(OH)_(d-3)(O—)₂]_(1/3),[—OG⁴(OH)_(d-4)(O—)₃]_(1/4) and so on, respectively.

In another embodiment herein, the ratio of m to n is specifically fromabout 20:1 to about 0.05 to 1, more specifically from about 5:1 to about0.2:1, and most specifically from about 2:1 to about 0.5:1.

In accordance with another embodiment herein, a process for thepreparation of an mercaptofunctional silane containinghydroxyalkyloxysilyl groups, cyclic and/or bridging dialkoxysilyl groupsand hydrocarbyl and/or heterocarbyl functionality groups is providedwhich comprises blending at least one hydrocarbyl functional silane ofthe formula:

G¹-(SiX₃)_(s)  (1)

and/or heterocarbyl functional silane of the formula:

[G³-(YG²)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

with at least one mercaptofunctional silane of the formula:

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein each occurrence of G¹, G², G³, Y, X, j, k, r, and s have one ofthe aforestated meanings and with the proviso that at least one of X isa hydrolyzable group; and transesterifying the mixture with one or morepolyhydroxy-containing compounds of the general formula (6):

G⁴(OH)_(d)  (6)

wherein each occurrence of G⁴ and d have one of the aforestatedmeetings; and advantageously in the presence of a transesterificationcatalyst.

In still another embodiment herein, a process for the preparation of anmercaptofunctional silane containing cyclic and/or bridging dialkoxysilyl groups and hydrocarbyl and/or heterocarbyl functionality isprovided which comprises blending at least one hydrocarbyl functionalsilane of the formula:

G¹-(SiX₃)_(s)  (1)

and/or heterocarbyl functional silane of the formula:

[G³-(YG²)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

with at least one mercaptofunctional silane of the formula:

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein each occurrence of G¹, G², G³, Y, X, j, k, r, and s have one ofthe aforestated meanings and with the proviso that at least one of X isa hydrolyzable group, and transesterifying the mixture with one or morediols of the general Formulae (7) and (8):

HO(R⁰CR⁰)_(f)OH  (7)

HO(CR⁰ ₂CR⁰ ₂O)_(e)H  (8)

wherein R⁰, e, and f have one of the aforestated meanings. In stillanother embodiment, the diol is HO(R⁰CR⁰)_(f)OH wherein R⁰ and f haveone of the aforestated meetings.

In one embodiment herein in connection with silanes of Formulae (10) and(11), the terms “diol” and “difunctional alcohol” refer to any structureof the general Formula (7):

HO(R⁰CR⁰)_(f)OH  (7)

wherein f and R⁰ are as defined herein. In one embodiment, thesestructures represent hydrocarbons in which two hydrogen atoms arereplaced with —OH in accordance with compounds of Formula (7), supra.

In another embodiment herein in connection with silanes of Formulae (10)and (11), “dialkoxy” and “difunctional alkoxy” refer tohydrocarbon-based diols in which the two OH hydrogen atoms have beenremoved to give divalent radicals, and whose structures are representedby the general formula:

—O(R⁰CR⁰)_(f)O—  (12)

wherein f and R⁰ are as defined herein.

In yet another embodiment herein in connection with silanes of Formulae(10) and (11), “cyclic dialkoxy” refers to a silane or group in whichcyclization is about a silicon atom by two oxygen atoms each of which isattached to a common divalent hydrocarbon group such as is commonly thecase with diols. In one embodiment cyclic dialkoxy groups herein arerepresented by Z^(θ). In one embodiment the structure of Z^(θ) isimportant in the formation of the cyclic structure. In yet one moreembodiment R⁰ groups that are more sterically hindered than hydrogenpromote the formation of cyclic structures. In yet even one moreembodiment the formation of cyclic structures is also promoted when thevalue of f in diol of Formula (7) is 2 or 3, and more specifically 3.

In yet a further embodiment herein in connection with silanes ofFormulae (10) and (11), “bridging dialkoxy” refers to a silane or groupin which two different silicon atoms are each bound to one oxygen atom,which in turn is bound to a common divalent hydrocarbon group such as iscommonly found in diols. Bridging dialkoxy groups herein are representedby Z^(β).

In yet still a further embodiment herein in connection with silanes ofFormulae (10) and (11), “hydroxyalkoxy” refers to a silane or group inwhich one OH hydrogen atom has been removed to provide a monovalentradical, and whose structures are represented by the general Formulae(13), (14) and (15):

(HO)_(d-1)G⁴O—  (13)

HO(R⁰CR⁰)_(f)O—  (14)

HO(CR⁰ ₂CR⁰ ₂O)_(e)—  (15)

wherein G⁴, e, f and R⁰ are defined as herein. Hydroxyalkoxy groupsherein are represented by X^(α).

In yet even another embodiment herein in connection with silanes ofFormula (10) and (11), the term “hydrocarbon based diols” refers todiols that contain two OH groups as part of a hydrocarbon structure. Inanother embodiment, absent from these hydrocarbon based diols areheteroatoms (other than the oxygens in the OH groups), in particularether groups. In one embodiment, hydrocarbon diols that containheteroatoms, such as oxygen, are represented by the Formula (8):

HO(CR⁰ ₂CR⁰ ₂O)_(e)—H  (8).

In another embodiment, these diols are not as likely to form cyclicstructures with the silyl group because of the size of the ring being 8atoms or larger, which are less likely to form than rings that contain 5or 6 atoms.

In yet an even further embodiment structure of Formula (7) will bereferred to herein as either “the appropriate diol” or “glycol” prefixedby the particular hydrocarbon group associated with the two OH groups.In one specific embodiment, some non-limiting examples of Formula (7)include neopentylglycol, 1,3-butanediol, 2-methyl-1,3-propanediol and2-methyl-2,4-pentanediol.

In yet even another specific embodiment, structure of Formula (12) willbe referred to herein as the appropriate dialkoxy, prefixed by theparticular hydrocarbon group associated with the two OH groups. In onespecific embodiment, thus, for example, the diols, neopentylglycol,1,3-butanediol, and 2-methyl-2,4-pentanediol correspond herein to thedialkoxy groups, neopentylglycoxy, 1,3-butanedialkoxy,2-methyl-1,3-propanediol and 2-methyl-2,4-pentanedialkoxy, respectively.

In a further embodiment herein for Z^(β), the notations,[—OG⁴(OH)_(d-2)O—]_(0.5), [—O(R⁰CR⁰)_(f)O—]_(0.5), and [—O(CR⁰ ₂CR⁰₂O)_(e)—]_(0.5) refer to one-half of a bridging dialkoxy group which canconnect to different silyl groups present in the mercaptofunctionalsilanes of Formulae (10) and (11). In one embodiment, these notationsare used in conjunction with a silicon atom and they are taken herein tomean that one-half of a dialkoxy group is bound to the particularsilicon atom. It is understood that the other half of the dialkoxy groupis bound to a silicon atom that occurs somewhere else in the overallmolecular structure being described. Thus, in one embodiment, the[—OG⁴(OH)_(d-2)O—]_(0.5), [—O(R⁰CR⁰)_(f)O—]_(0.5), and [—O(CR⁰ ₂CR⁰₂O)_(e)—]_(0.5) dialkoxy groups mediate the chemical bonds that hold twoseparate silicon atoms together, whether these two silicon atoms occurintermolecularly or intramolecularly. In one embodiment, in the case of[—O(R⁰CR⁰)_(f)O—]_(0.5) and [—O(CR⁰ ₂CR⁰ ₂O)_(e)—]_(0.5), if the group(R⁰CR⁰)_(f) and (CR⁰ ₂CR⁰ ₂O)_(e) are unsymmetrical, either end of[—O(R⁰CR⁰)_(f)O—]_(0.5) and [—O(CR⁰ ₂CR⁰ ₂O)_(e)—]_(0.5) can be bound toeither of the two silicon atoms required to complete the structures ofsilanes of Formulae (10) and (11).

In a still further embodiment herein in connection with silanes ofFormulae (1), (2), (3), (10) and (11), “alkyl” includes straight,branched and cyclic alkyl groups; “alkenyl” includes any straight,branched, or cyclic alkenyl group containing one or more carbon-carbondouble bond, where the point of substitution can be either at acarbon-carbon double bond or elsewhere in the group; and “alkynyl”includes any straight, branched, or cyclic alkynyl group containing oneor more carbon-carbon triple bonds and, optionally, one or morecarbon-carbon double bonds as well, where the point of substitution canbe either at a carbon-carbon triple bond, a carbon-carbon double bond,or elsewhere in the group. Specific examples of alkyls include, but arenot limited to, methyl, ethyl, propyl and isobutyl. Specific examples ofalkenyls include, but are not limited to, vinyl, propenyl, allyl,methallyl, ethylidenyl norbornane, ethylidene norbornyl, ethylidenylnorbornene and ethylidene norbornenyl. Specific examples of alkynylsinclude, but are not limited to, acetylenyl, propargyl andmethylacetylenyl.

In one embodiment herein in connection with silanes Formulae (1), (2),(3), (10) and (11), “aryl” includes the non-limiting group of anyaromatic hydrocarbon from which one hydrogen atom has been removed;“aralkyl” includes, but is not limited to, any of the aforementionedalkyl groups in which one or more hydrogen atoms have been substitutedby the same number of like and/or different aryl (as defined herein)substituents; and “arenyl” includes the non-limiting group of any of theaforementioned aryl groups in which one or more hydrogen atoms have beensubstituted by the same number of like and/or different alkyl (asdefined herein) substituents. Specific examples of aryls include, butare not limited to, phenyl and naphthalenyl. Specific examples ofaralkyls include, but are not limited to, benzyl and phenethyl. Specificexamples of arenyls include, but are not limited to, tolyl and xylyl.

In another embodiment herein, in connection with silanes of Formulae(1), (2), (3), (10) and (11), “cyclic alkyl”, “cyclic alkenyl”, and“cyclic alkynyl” also include bicyclic, tricyclic, and higher cyclicstructures, as well as the aforementioned cyclic structures furthersubstituted with alkyl, alkenyl, and/or alkynyl groups. Representativeexamples of “cyclic alkyl”, “cyclic alkenyl”, and “cyclic alkynyl”include, but are not limited to, norbornyl, norbornenyl, ethylnorbornyl,ethylnorbornenyl, ethylcyclohexyl, ethylcyclohexenyl,cyclohexylcyclohexyl and cyclododecatrienyl.

In one embodiment some representative examples of the functional groups(—Y—) present in the silanes of the present invention include, but arenot limited to, carboxylate ester, —C(═O)—O— and —OC(═O)— (any silanewith this functional group is a “carboxylate ester silane”); ketone,—C(═O)— (any silane with this functional group is a “ketonic silane”;thioketone, —C(═S)— (any silane with this functional group is a“thioketonic silane”); carbonate ester, —O—C(═O)—O— (any silane withthis functional group is a “carbonate ester silane”); amide, —C(═O)NR—and —NRC(═O)— (any silane with this functional group is a“amidosilane”); ether, —O— (any silane with this functional group is a“ether silane”); amine, —NR— (any silane with this functional group is a“aminosilane”); urea, —NRC(═O)NR— (any silane with this functional groupis a “ureidosilane”); thio, —S— (any silane with this functional groupis a “sulfidosilane”); and guanidine, (—NR)C(═NR)NR— (any silane withthis functional group is a “guanidinosilane”). In another embodimentherein, each occurrence of Y is selected independently from the groupconsisting of —C(═NR)—; —(C═O)—; (—NR)C(═O)—; —OC(═O)—; —OC(═S)—;—OC(═O)O—; —C(═S)—; —C(═O)O—;

(—NR)C(═O)(NR—); (—NR)C(═NR)(NR—); —O—; —S—; —SS—; and —NR—. In stillanother embodiment herein, Y is a non-limiting selection, selected fromthe group consisting of —O—; —NR—; —C(═O)O—; —C(═O)NR— and(—NR)C(═O)(NR—).

In another embodiment herein, the silane is one described by Formula(11) in which Y is —O— or —NR—, G² is a divalent or polyvalent groupderived by substitution of C₁-C₁₂ alkyl; G³ is hydrogen or C₁ to C₁₂straight chain alkyl; Z^(θ) is [—O(R⁰CR⁰)_(f)O—]_(0.5) and Z^(θ) is—O(R⁰CR⁰)_(n)O— wherein R⁰ is hydrogen or methyl and f is 2 or 3, m andn are 1 to about 5, k is 1 to about 5, j is 1 and r is 1 to about 2.

In still another embodiment herein, the silane is one described byFormula (10) in which G¹ is a monovalent straight chain group derivedfrom a C₃-C₁₀ alkyl, and G² is a divalent or polyvalent group derived bysubstitution of a C₁-C₁₀ alkyl, Z^(θ) is [—O(R⁰CR⁰)_(f)O—]_(0.5) andZ^(θ) is —O(R⁰CR⁰)_(f)O— wherein R⁰ is hydrogen or methyl and f is 2 or3, m and n are 1 to about 5 and r is 1 to about 2.

In yet another embodiment herein, silane is one in which both thesilanes of Formulae (10) and (11) are present; such as wherein both thesilanes of Formulae (10) and (11) are mixed together.

In one embodiment some representative examples of G¹ include, but arenot limited to, CH₃(CH₂)_(g)—, wherein g is 1 to about 29; benzyl;2-phenylethyl; cyclohexyl; any of the isomers of

—CH₂CH₂-norborane; any of the isomers of —CH₂CH₂-cyclohexane; branchedalkyl groups of 1 to 30 carbon atoms and include the non-limitingexamples such as CH₃(CH₂)₄CH(CH₂CH₃)CH₂—, CH₃CH₂CH(CH₂CH₃)CH₂—,CH₃CH(CH₃)CH₂—, CH₃CH₂CH(CH₃)CH₂—, and CH₃(CH₂)₄CH(CH₃)CH₂—;and any of the monoradicals obtainable from norbornane, cyclohexane,cyclopentane, tetrahydrodicyclopentadiene, or cyclododecene by loss ofone hydrogen atom.

In one specific embodiment some representative examples of G² include,but are not limited to those selected from the group consisting ofdiethylene cyclohexane; 1,2,4-triethylene cyclohexane; phenylene; any ofthe structures derivable from divinylbenzene, such as the non-limitingexamples of

—CH₂CH₂(C₆H₄)CH₂CH₂— and —CH₂CH₂(C₆H₄)CH(CH₃)—, where the notation C₆H₄denotes a disubstituted benzene ring; any of the structures derivablefrom dipropenylbenzene, such as the non-limiting examples of—CH₂CH(CH₃)(C₆H₄)CH(CH₃)CH₂—, where the notation C₆H₄ denotes adisubstituted benzene ring; any of the structures derivable frompiperylene, such as the non-limiting examples of —CH₂CH₂CH₂CH(CH₃)—,—CH₂CH₂CH(CH₂CH₃)—, and

—CH₂CH(CH₂CH₂CH₃)—; any of the isomers of —CH₂CH₂-norbornyl-; any of thediradicals obtainable from tetrahydrodicyclopentadiene or cyclododeceneby loss of two hydrogen atoms; any of the structures derivable fromlimonene, such as the non-limiting example of, —CH₂CH(4-CH₃-1-C₆H₉—)CH₃,where the notation C₆H₉ denotes isomers of the trisubstitutedcyclohexane ring lacking substitution in the 2 position; any of themonovinyl-containing structures derivable from trivinylcyclohexane, suchas the non-limiting examples of —CH₂CH₂(vinylC₆H₉)CH₂CH₂— and—CH₂CH₂(vinylC₆H₉)CH(CH₃)—, where the notation C₆H₉ denotes any isomerof the trisubstituted cyclohexane ring; any of the monounsaturatedstructures derivable from myrcene containing a trisubstituted C═C, suchas the non-limiting examples of

—CH₂CH[CH₂CH₂CH═C(CH₃)₂]CH₂CH₂—, —CH₂CH[CH₂CH₂CH═C(CH₃)₂]CH(CH₃)—,—CH₂C[CH₂CH₂CH═C(CH₃)₂](CH₂CH₃)—, —CH₂CH₂CH[CH₂CH₂CH═C(CH₃)₂]CH₂—,—CH₂CH₂(C—)(CH₃)[CH₂CH₂CH═C(CH₃)₂], and—CH₂CH[CH(CH₃)[CH₂CH₂CH═C(CH₃)₂]]—; and any of the monounsaturatedstructures derivable from myrcene lacking a trisubstituted C═C, such asthe non-limiting examples of —CH₂CH(CH═CH₂)CH₂CH₂CH₂C(CH₃)₂—,—CH₂CH(CH═CH₂)CH₂CH₂CH[CH(CH₃)₂]_, —CH₂C(═CH—CH₃)CH₂CH₂CH₂C(CH₃)₂—,—CH₂C(═CH—CH₃)CH₂CH₂CH[CH(CH₃)₂]_, —CH₂CH₂C(═CH₂)CH₂CH₂CH₂C(CH₃)₂—,—CH₂CH₂C(═CH₂)CH₂CH₂CH[CH(CH₃)₂]_, —CH₂CH═C(CH₃)₂CH₂CH₂CH₂C(CH₃)₂— and—CH₂CH═C(CH₃)₂CH₂CH₂CH[CH(CH₃)₂]; —(CH₂)_(g)— wherein g is preferably aninteger of from 1 to 30, which represent terminal straight-chain alkylsfurther substituted terminally at the other end, such as thenon-limiting examples of —CH₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, and—CH₂CH₂CH₂CH₂CH₂CH₂CH₂CH₂—, and their beta-substituted analogs, such as—CH₂(CH₂)₂CH(CH₃)—, where i is preferably 0 to 16; methyl substitutedalkylene groups such as the non-limiting examples of—CH₂CH₂-cyclohexyl-, —CH₂CH₂C(CH₃)₂CH₂—, —CH₂CH(CH₃)CH₂—, any of thestructures derivable from isoprene, such as —CH₂CH(CH₃)CH₂CH₂—,

—CH₂CH(CH₃)CH(CH₃)—, —CH₂C(CH₃)(CH₂CH₃)—, —CH₂CH₂CH(CH₃)CH₂—,—CH₂CH₂C(CH₃)₂— and —CH₂CH[CH(CH₃)₂]_; any structure derivable frommethallyl chloride; any of the structures derivable from butadiene, suchas the nonlimiting examples of —CH₂CH₂CH₂CH₂—, —CH₂CH₂CH(CH₃)—, and—CH₂CH(CH₂CH₃)—; and, any of the diradicals obtainable from norbornane,cyclohexane, or cyclopentane, by loss of two hydrogen atoms.

In another embodiment herein, some representative examples of G³include, but are not limited to, hydrogen, CH₃(CH₂)_(g)—, wherein g is 1to about 29; benzyl; 2-phenylethyl; cyclohexyl; any of the isomers of—CH₂CH₂-norborane; any of the isomers of —CH₂CH₂-cyclohexane; branchedalkyl groups of 1 to 30 carbon atoms such as the non-limiting examplesincluding CH₃(CH₂)₄CH(CH₂CH₃)CH₂—, CH₃CH₂CH(CH₂CH₃)CH₂—, CH₃CH(CH₃)CH₂—,CH₃CH₂CH(CH₃)CH₂—, CH₃(CH₂)₄CH(CH₃)CH₂—, and any of the monoradicalsobtainable from norbornane, cyclohexane, cyclopentane,tetrahydrodicyclopentadiene, or cyclododecene by loss of one hydrogenatom.

In another embodiment herein, the silanes of Formula (10) and (11) havestructures in which the sum of the carbon atoms in the hydrocarbyland/or heterocarbyl groups that are determined by adding up the carbonatoms in the G¹, G² and G³ groups is specifically from about 3 to about18 more specifically from about 6 to about 14, and most specifically offrom about 8 to about 12. In one embodiment, the amount of carbon inthese fragments facilitates the dispersion of filler into the organicpolymers, thereby improving the balance of properties in the curedfilled rubber.

In yet another embodiment herein, G¹ is CH₃CH₂CH₂CH₂CH₂CH₂CH₂— and G² is—CH₂CH₂CH₂—, r is 1 and s is 1.

In yet a further embodiment, some representative non-limiting examplesof R and R⁰ groups are hydrogen, branched and straight-chain alkyls of 1to 18 carbon atoms or more, such as the non-limiting examples of methyl,ethyl, propyl, isopropyl, butyl, octenyl, cyclohexyl, phenyl, benzyl,tolyl and allyl.

In one embodiment, R groups are selected from C₁ to C₄ alkyls andhydrogen and R⁰ groups are selected from hydrogen, methyl, ethyl andpropyl.

In one other embodiment, some specific non-limiting examples of X^(α)are methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, oximato,monovalent hydroxyalkoxy groups derived from diols, —O(R⁰CR⁰)_(f)OHwhere R⁰ and f is defined as herein, such as the non-limiting examplesof 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxy-2,2-dimethylpropoxy,3-hydroxypropoxy, 3-hydroxy-2-methylpropoxy, 3-hydroxybutoxy,4-hydroxy-2-methylpent-2-oxy, and 4-hydoxybut-1-oxy and monovalent etheralkoxy groups of the general Formulae (16), (17), and (18):

(R¹O)_(d-1)G⁴O—  (16)

R¹(R⁰CR⁰)_(r)O—  (17)

R¹(CR⁰ ₂CR⁰ ₂O)_(e)—  (18)

wherein R¹ is independently selected from the group consisting ofstraight, cyclic or branched alkyl groups that can or can not containunsaturation, alkenyl groups, aryl groups and aralkyl groups thatcontain from 1 to 18 carbon atoms; and R⁰, G⁴, e and f are defined asherein. In one embodiment X^(α) can also be a monovalent alkyl group,such as the non-limiting examples of methyl and ethyl.

In a specific embodiment, X^(α) is one of the non-limiting examples ofmethoxy, ethoxy, acetoxy, methyl, ethyl, 2-hydroxyethoxy,2-hydroxypropoxy, 3-hydroxy-2,2-dimethylpropoxy, 3-hydroxypropoxy,3-hydroxy-2-methylpropoxy, 3-hydroxybutoxy,4-hydroxy-2-methylpent-2-oxy, and 4-hydoxybut-1-oxy.

In one embodiment, some specific non-limiting examples of Z^(β) andZ^(θ) are the divalent alkoxy groups derived from diols such as ethyleneglycol, propylene glycol, neopentyl glycol, 1,3-propanediol,2-methyl-1,3-propanediol, 1,3-butanediol, 2-methyl-2,4-pentanediol,1,4-butanediol, cyclohexane dimethanol and pinacol. In anotherembodiment, some more specific non-limiting examples of Z^(β) and Z^(θ)are divalent alkoxy groups derived from ethylene glycol, propyleneglycol, neopentyl glycol, 1,3-propanediol, 2-methyl-1,3-propanediol,1,3-butanediol and 2-methyl-2,4-pentanediol.

In one specific embodiment herein, Z^(β) and Z^(θ) are divalent alkoxygroups derived from 1,3-propanediol, 2-methyl-1,3-propanediol,1,3-butanediol, and 2-methyl-2,4-pentanediol and combinations thereof.In one embodiment, the cyclic dialkoxy content of the silanes hereinshould be kept sufficiently high relative to the total dialkoxy contentpresent to prevent excessive crosslinking, which would lead togellation. In one embodiment herein, the cyclic dialkoxy silyl contentof the silanes can specifically be from about 10 to about 100 molepercent of the total concentration of silyl groups, more specificallyfrom about 25 to about 90 mole percent of the total concentration ofsilyl groups and most specifically from about 50 to about 70 molepercent of the total concentration of silyl groups. In anotherembodiment herein, excessive crosslinking can also be avoided if X^(α)in the structure of Formulae (10) and (11), as indicated by thecoefficient u, is large, such as for example, specifically, from about 1to about 2. In one embodiment, v and w in Formulae (10) and (11) aresuch that the ratio v/w is specifically between 0 and 1. In anotherembodiment, u is from 1 to about 2 with the proviso that u+v+2w=3.

In yet a further embodiment, some representative non-limiting examplesof the mercaptofunctional silanes herein, such as those that containcyclic and/or bridging dialkoxysilyl groups, mercapto groups andhydrocarbylsilane and/or heterocarbylsilane include, but are not limitedto,3-{4-methyl-2-[2-(4-methyl-2-pentyl-[1,3,2]dioxasilolan-2-yloxy)-propoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol;3-{2-[2-(2-methyl-[1,3,2]dioxasilolan-2-yloxy)-ethoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol;mixture of3-[2-(3-mercapto-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propan-1-ol and3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propan-1-ol;4-{2-[3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-[1,3,2]dioxasilinan-2-yl}-butane-1-thiol;4-[2-(3-{2-[3-(2-methoxy-ethoxy)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol;4-[5-methyl-2-(2-methyl-3-{5-methyl-2-[3-(2-methylamino-ethylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol;2-acetylamino-N-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-acetamide;(2-{3-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-ureido}-ethyl)-urea;4-acetoxy-butyric acid3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propylester; carbonic acid2-[3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propoxycarbonyloxy]-ethylester methyl ester;4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-dimethyl-silanyl}-butane-1-thiol;4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-diethoxy-silanyl}-butane-1-thiol;4-[butyl-[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-(4-mercapto-butyl)-silanyloxy]-2-methyl-pentan-2-ol;4-{(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyl}-2-methyl-butan-1-ol;3-{(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyloxy}-2-methyl-propan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyl]-2-methyl-butan-1-ol;3-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyloxy]-2-methyl-propan-1-ol;3-[{3-[(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-methyl-octyl-silanyloxy]-3-methyl-butyl}-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propan-1-ol;4-((3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-octyl-silanyl)-2-methyl-butan-1-ol;3-((3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-octyl-silanyl)-2-methyl-propan-1-ol;4-(benzyl-(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-phenethyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-silanyl)-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-pent-4-enyl-silanyl]-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-octyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol;and combinations thereof.

In an even further embodiment herein, organofunctional silanecompositions herein that contain cyclic and/or bridging silyl groups andboth mercaptan and hydrocarbyl and/or heterocarbyl groups normally havea random distribution of mercapto and hydrocarbyl and/or heterocarbylgroups within the individual silane. However, in one specific embodimentherein silanes can be prepared in which the mercaptan groups aresegregated. In a more specific embodiment this segregation will resultin compositions where the nearest neighbors to a mercaptan group areother mercaptan groups or the nearest neighbors to a hydrocarbyl and/orheterocarbyl group are other hydrocarbyl and/or heterocarbyl groups. Inone specific embodiment, the segregation of the mercaptan groups canoccur when hydrocarbyl and/or heterocarbyl cyclic and/or bridged silanesare physically mixed with mercaptofunctional cyclic and/or bridgedsilanes.

Moreover, in one other embodiment herein, it is understood that thesesilane compositions can also contain mercaptofunctional and hydrocarbyland/or heterocarbyl silane components that contain only monofunctionalalkoxy groups. In a further embodiment herein, mercaptofunctionalsilanes, hydrocarbylsilane and/or heterocarbylsilane containing onlymonofunctional alkoxy groups can be used as reagents in the preparationof the silanes herein. However, it is understood in one embodiment thatthese monofunctional alkoxy groups can contribute to VOC emissionsduring use if the monofunctional alcohols that are form upon hydrolysisof the silanes have high vapor pressure at room temperature. In afurther embodiment, some non-limiting examples of high boilingmonofunctional alkoxy groups, are those such as the alkoxy groups whosestructures are represented by formula

R¹(CR⁰ ₂CR⁰ ₂O)_(e)—  (18)

wherein R⁰, R¹ and e are defined as herein. In another embodiment,moreover, it is understood that the partial hydrolyzates and/orcondensates of these cyclic and/or bridging mercaptofunctional andhydrocarbyl and/or heterocarbyl silanes (i.e., cyclic and/or bridgingdialkoxy mercaptofunctional and hydrocarbyl or heterocarbyl siloxanesand/or silanols) can also be encompassed by the silanes herein, in thatthese partial hydrolyzates and/or condensates will be a side product ofmost methods of manufacture of the silanes described herein or can occurupon storage, especially in humid conditions, or under conditions inwhich residual water remaining from their preparation is not completelyremoved subsequent to their preparation.

Furthermore in another specific embodiment, partial to substantialhydrolysis of silanes of Formula (10) and (11) will form silanes thatcontain siloxane bonds, i.e., Z^(β)=(—O—)_(0.5), and are encompassed bythe silanes described herein; and in a more specific embodiment they canbe deliberately prepared by incorporating the appropriate stoichiometryor an excess of water into the methods of preparation described hereinfor the silanes. In one embodiment, silane structures hereinencompassing hydrolyzates and siloxanes are described in the structuresrepresented by Formulae (10) and (11) wherein the subscripts, ν, ofZ^(β)=(—O—)_(0.5) and/or u of X^(α)═OH are substantive (i.e.,substantially larger than zero), for example, where v is specifically offrom about 1 to about 2, and more specifically of about 1; and/orwherein u is specifically of from about 0 to about 2, more specificallyof from about 0 to about 1 and most specifically of about 1 and with theproviso that the silane of Formulae (10) and (11) contain at least oneZ^(β) that is [—OG⁴(OH)_(d-2)O—]_(0.5) or at least one Z^(θ) that is—O(R⁰CR⁰)_(f)O—. In one embodiment herein, the ratio of siloxanebridging group, (—O—)_(0.5), to dioxy bridging group,[—O(R⁰CR⁰)_(f)O—]_(0.5), is within a range of from about 0 to about 1.In another embodiment, the ratio is within a range of from about 0 toabout 0.2. In a further embodiment, the ratio is within a range of fromabout 0.05 to about 0.15.

In another embodiment herein, the organofunctional silanes herein,including their mixtures, can be loaded on a particulate carrier such asthe non-limiting examples of a porous polymer, carbon black, a siliceousmaterial such as silica, and the like, so that they are in solid formfor addition to rubber in a rubber compounding operation.

In one embodiment herein there is provided a process for making amercaptofunctional silane composition which comprises:

-   -   reacting at least one mercapto functional silane possessing at        least one transesterifiable silyl group and at least one        hydrocarbylsilane and/or heterocarbylsilane possessing at least        one transesterifiable silyl group, with at least one        polyhydroxy-containing compound under transesterification        conditions to provide said mercaptofunctional silane composition        wherein said mercaptofunctional silane composition contains at        least one organofunctional silane selected from the group        consisting of:        (i) mercaptosilane possessing at least one hydroxyalkoxysilyl        group and/or a cyclic dialkoxysilyl group,        (ii) hydrocarbylsilane or heterocarbylsilane possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,        (iii) mercaptosilane dimer in which the silicon atoms of the        mercaptosilane units are bonded to each other through a bridging        dialkoxy group, each silane unit optionally possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,        (iv) hydrocarbylsilane and/or heterocarbylsilane dimer in which        the silicon atoms of the hydrocarbylsilane and/or        heterocarbylsilane units are bonded to each other through a        bridging dialkoxy group, each silane unit optionally possessing        at least one hydroxyalkoxysilyl group and/or a cyclic        dialkoxysilyl group,        (v) silane dimer possessing a mercaptosilane unit, the silicon        atom of which is bonded to the silicon atom of a        hydrocarbylsilane or heterocarbylsilane unit through a bridging        dialkoxy group, each silane unit optionally possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,        (vi) mercaptosilane oligomer in which the silicon atoms of        adjacent mercaptosilane units are bonded to each other through a        bridging dialkoxy group, the terminal mercaptosilane units        possessing at least one hydroxyalkoxysilyl group and/or a cyclic        dialkoxysilyl group,        (vii) hydrocarbylsilane and/or heterocarbylsilane oligomer in        which the silicon atoms of adjacent hydrocarbylsilane or        heterocarbylsilane units are bonded to each other through a        bridging dialkoxy group, the terminal hydrocarbylsilane and/or        heterocarbylsilane units possessing at least one        hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,        and

(viii) silane oligomer possessing at least one mercaptosilane unit andat least one hydrocarbylsilane or heterocarbylsilane unit, the siliconatoms of adjacent silane units being bonded to each other through abridging dialkoxy group, the terminal silane units possessing at leastone hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group, withthe provisio that,

where the mercaptofunctional silane composition resulting from thisprocess contains one or more of (i), (iii) and (vi), the compositionadditionally contains one or more of (ii), (iv), (v), (vii) and (viii),and where the mercaptofunctional silane composition resulting from thisprocess contains one or more of (ii), (iv) and (vii), the compositionadditionally contains one or more of (i), (iii), (v), (vi) and (viii).

In a further embodiment herein, mercaptofunctional silanes of Formulae(10) and (11) herein and mixtures thereof can be prepared by the generalpreparative process described as herein of which there are numerousspecific embodiments. Generally, in one embodiment, the processembodiments for making one or a mixture of silanes of Formulae (10) and(11) involve a transesterification reaction between one or morealkoxysilane Formulae (1), (2) and (3) and one or morepolyhydroxy-containing compounds of Formula (6), (7) or (8).

In one embodiment, the process for preparing the mercapto functionalsilanes of Formula (10) and/or (11) comprises:

a.) mixing hydrocarbyl and/or heterocarbyl silanes of the generalFormulae (1) and/or (2):

G¹-(SiX₃)_(s)  (1)

and/or

[G³-(YG²)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

with a mercaptosilane of general Formula (3):

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein each occurrence of G¹, G², G³, Y, X, j, k, r, and s are definedas herein, and with the proviso that at least one of X is a hydrolyzablegroup, andb.) transesterifying this mixture with at least one diol having thestructure G⁴(OH)_(d), HO(R⁰CR⁰)_(f)OH, or HO(CR⁰ ₂CR⁰ ₂O)_(e)—H,optionally in the presence of a transesterification catalyst; andremoving the X—H group that is formed; wherein each occurrence of G⁴,R⁰, d, e and fare defined as herein.

In one embodiment, the first reaction can be carried out by reacting amixture of mercaptofunctional alkoxy silane, a hydrocarbyl and/orheterocarbyl silane with a diol at a molar ratio of about 0.1 mole toabout 3.0 moles of diol per 1 mole of silyl group to be transesterified.In another embodiment, the ratio can range from about 1.0 to about 2.5for a trialkoxysilyl group. In yet a further embodiment, the ratio canrange from about 1.5 to about 2.0 for a trialkoxysilyl group. In oneembodiment, the reaction can be carried out at a temperature rangingfrom specifically about 0 to about 150° C., more specifically about 25°C. to about 100° C. and most specifically about 60° C. to about 80° C.and all subranges therebetween while maintaining a pressure in the rangeof from about 0.1 to about 2000 mm Hg absolute. In one embodiment, thetemperature can range from about 30° C. to about 90° C. and allsubranges therebetween. In another embodiment, the pressure can rangefrom about 1 to about 80 mm Hg absolute. As those skilled in the artwill recognize, in one embodiment, excess diol can be utilized toincrease reaction rate, but it is not necessary under these conditionsas it can increase the cost. In another embodiment, the reaction can becarried out by slowly adding diol to the mixture of themercaptofunctional alkoxysilane and hydrocarbyl and/or heterocarbylsilane at the desired reaction temperature and vacuum. In anotherembodiment, as the lower boiling X—H group, such as the mono alcohol, isformed, it can be removed from the reaction mixture by a distillationcycle and removal of the mono alcohol helps drive the reaction tocompletion. In one embodiment, the reactions optionally can be catalyzedusing a transesterification catalyst. In yet a further embodiment,suitable tranesterification catalysts are strong protic acids whosepK_(a) are below 5.0, transition metal complexes such as complexes oftin, iron, titanium and other metal catalysts. In one embodiment,catalysts suitable for these reaction are disclosed in, “The SiloxaneBond, Physical Properties and Chemical Transformations”, M. G. Voronkov,V. P. Mileshkevich and Yu. A. Yuzhelevskii, Consultants Bureau, adivision of Plenum Publishing Company, New York (1978), Chapter 5 and isincorporated by reference herein in its entirety. In a furtherembodiment, strong bases are generally unsuitable as transesterificationcatalysts since they promote the reaction of the mercaptofunctionalgroup with the diol and result in the formation of sulfides. In oneembodiment, the acid or metal catalysts can be used at a range ofspecifically from about 10 ppm to about 2 weight percent, morespecifically from about 20 ppm to about 1000 ppm, and most specificallyof from about 100 ppm to about 500 ppm.

In a further embodiment herein, the final mixture can optionally bebuffered after the reaction is complete. In one specific embodiment,buffering the mixture will neutralize the strong protic acids andthereby be less corrosive to metals and add to long-term productstability. In a still further specific embodiment, buffering can beconducted through methods and compounds known in the art.

In one specific embodiment, the products of the transesterification ofmercaptofunctional and hydrocarbyl and/or heterocarbyl silanes cancomprise a considerable fraction of monomeric material in addition tothe formation of dimers and other cyclic and/or bridged oligomers asillustrated by low viscosity reaction products. In one specificembodiment the fraction of monomeric material is of from about 1 toabout 99 mole percent, more specifically of from about 10 to about 50mole percent, and most specifically of from about 15 to about 25 molepercent.

In a further embodiment, the process for making the organofunctionalsilane compositions herein can optionally employ an inert solvent. In aspecific embodiment, the solvent can serve as a diluent, carrier,stabilizer, refluxing aid or heating agent. In a more specificembodiment, generally, any inert solvent that does not enter into thereaction or adversely affect the preparative process can be used. In oneembodiment, the solvents are liquid under normal conditions and have aboiling point below about 150° C. In a more specific embodiment, somenon-limiting examples of suitable solvents include aromatic or aliphatichydrocarbon, ether, aprotic, or chlorinated hydrocarbon solvents such astoluene, xylene, hexane, butane, diethyl ether, dimethylformamide,dimethyl sulfoxide, carbon tetrachloride, methylene chloride, andcombinations thereof.

In one embodiment herein, the process of transesterifying thealkoxysilane with polyhydroxy-containing compound can be conductedcontinuously. In one more embodiment, in the case of a continuousoperation, the process comprises:

-   -   a) reacting, in a thin film reactor, a thin film reaction medium        comprising a mixture of at least one silane of Formulae (1)        or (2) and a mercaptosilane of Formula (3), with at least one        polyhydroxy-containing compound of Formula (6) and, optionally,        transesterification catalyst, to provide mercapto and        hydrocarbyl and/or heterocarbyl functional silanes that contains        a cyclic and/or bridged dialkoxy group, and by-product mono        alcohol;    -   b) vaporizing by-product mono alcohol from the thin film to        drive the reaction;    -   c) optionally, recovering by-product mono alcohol by        condensation;    -   d) recovering the organofunctional silane reaction product(s);        and,    -   e) optionally, neutralizing the reaction medium to improve the        storage stability of the mercapto functional silane product(s)        therein.

In one embodiment herein, the molar ratio of polyhydroxy-containingcompound to the mixture of mercapto and hydrocarbyl and/or heterocarbylsilanes used in the continuous thin film process will depend upon thenumber of alkoxy groups that are desired to be replaced with apolyhydroxy-containing group, such as the non-limiting example of a diol(glycol). In one more specific embodiment, theoretically, a molar ratioof about 0.5 mole of diol of Formula (7) or (8) is required per mole ofalkoxy-silyl group to be transesterified to replace all of the monoalkoxy or other X-groups. In another embodiment herein, a molar ratio offrom about 0.1 to about 1.0 moles of diol can be used per mole ofalkoxy-silyl group. In yet another embodiment herein, a molar ratio offrom about 0.5 to about 1.0 moles of diol can be used per mole ofalkoxy-silyl group. In a further embodiment, and, in many cases,additional diol is desirable because in some cases only one of thehydroxyl groups of the diol reacts with the alkoxysilyl group. In oneembodiment these diols that react only once with a silyl group aredefined as X^(α) in Formulae (10) and (11). In a further embodiment, thediols, referred to herein as “hydroxyalkoxy”, reduce the viscosity andinhibit the gelation of the silane. In a still further embodiment and asone skilled in the art will readily recognize, excess diol can beutilized to increase reaction rates.

In one specific embodiment, the method of forming the film can be any ofthose known in the art. In a more specific embodiment, typical knowndevices include but are not limited to, falling film or wiped filmevaporators. In one specific embodiment, minimum film thickness and flowrates will depend on the minimum wetting rate for the film formingsurface. In another specific embodiment, maximum film thickness and flowrates will depend on the flooding point for the film and device. In astill further specific embodiment, the alcohol is vaporized from thefilm by heating the film, by reducing pressure over the film, or by acombination of both. In one embodiment, mild heating and reducedpressure are utilized to form the structures described herein. In yet afurther embodiment, optimal temperatures and pressures (partial vacuum)for running the processes described herein will depend upon the specificmercaptofunctional or hydrocarbyl or heterocarbyl silane's alkoxy groupsand the diol used in the process. In yet an even further embodiment,additionally if an optional inert solvent is used in the process, thatchoice will affect the optimal temperatures and pressures (partialvacuum) utilized. In one specific embodiment, some non-limiting examplesof such solvents include those listed herein. In one embodiment herein,the by-product X—H, such as a monofunctional alcohol, vaporized from thefilm is removed from the reactive distillation device by a standardpartial vacuum-forming device and can be condensed, collected, andrecycled as feed to other processes. In one embodiment, the silaneproduct is recovered by standard means from the reactive distillationdevice as a liquid phase. In another embodiment, if an inert solvent hasbeen used or if additional purification is necessary, the silane productcan be fed to another similar distillation device or distillation columnto effect that separation. In still another specific embodiment,optionally the transesterified reaction products can be neutralized toimprove product storage.

In another embodiment herein, a process for preparing themercaptofunctional silanes containing hydrocarbylsilane and/orheterocarbylsilane groups comprises:

-   -   a) transesterifying at least one mercaptofunctional silane of        chemical structure:

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein each occurrence of G², X, r, and s is as defined herein, andwith the proviso that at least one of X is a hydrolyzable group; with adiol or polyhydroxy compound, optionally in the presence of a catalyst;

-   -   b) optionally, removing the by-product X—H, such as mono        alcohol;    -   c) tranesterifying the hydrocarbyl and/or heterocarbylsilane or        mixture thereof of the chemical structure:

G¹-(SiX₃)_(s)  (1)

and/or

[G³-(YG²)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

wherein each occurrence of G¹, G², G³, Y, X, j, k and s is as definedherein and with the proviso that at least one of X is a hydrolyzablegroup with a diol or polyhydroxy compound, optionally in the presence ofa catalyst;

-   -   d) optionally, removing the by-product X—H, such as mono        alcohol;    -   e) and mixing the compounds from process (a) or (b) with the        compounds of process (c) or (d), optionally in a desired ratio;        and    -   f) optionally, neutralizing protonic transesterification        catalyst, if utilized, with a base.

In one embodiment herein, the amount of hydrocarbyl and/or heterocarbylsilane of chemical structures of Formulae (1) and/or (2):

G³-(SiX₃)_(s)  (1)

[G³-(YG²)_(k)Y]_(j)-G²-(SiX₃)_(s)  (2)

and the amount of mercaptofunctional silane of chemical structure ofFormula (3):

(HS)_(r)-G²-(SiX₃)_(s)  (3)

wherein each occurrence of G¹, G², G³, Y, X, j, k, r, and s is asdefined herein and with the proviso that at least one of the X is ahydrolyzable group, are mixed in a molar ratio of silanes of Formula (1)and/or (2) to silane Formula (3) in a range of specifically from about20:1 to about 0.05:1, more specifically from about 5:1 to about 0.2:1,and most specifically from about 2:1 to about 0.5:1.

In one more specific embodiment, if a protic catalyst is used to promotethe transesterification of the silanes with diol, it can be useful toneutralize the catalyst with a base to improve the product's stability;however, only a stoichiometric amount of base is required to neutralizethe protic catalyst; larger amounts of base will promote undesirableside reactions.

In one specific embodiment, it is understood that the desired ratio ofmercapto groups to the hydrocarbyl and/or heterocarbyl groups isdetermine by the mix ratio. In another specific embodiment, thestructure of the silane prepared can be bimodal in distribution. In yeta further specific embodiment, the oligomers and polymers formed canhave segments where the nearest neighbors of the mercapto group areother mercapto groups and likewise the nearest neighbors of thehydrocarbyl and/or heterocarbyl group are other hydrocarbyl and/orheterocarbyl groups. In one embodiment, the distribution of mercapto andhydrocarbyl and/or heterocarbyl groups is therefore not random.

Further in another embodiment, a free flowing filler composition isprovided which comprises:

-   -   a) at least one particulate filler; and,    -   b) a mercaptofunctional silane composition comprising at least        one organofunctional silane selected from the group consisting        of:    -   (i) mercaptosilane possessing at least one hydroxyalkoxysilyl        group and/or a cyclic dialkoxysilyl group,    -   (ii) hydrocarbyl and/or heterocarbyl silane possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,    -   (iii) mercaptosilane dimer in which the silicon atoms of the        mercaptosilane units are bonded to each other through a bridging        dialkoxy group, each silane unit optionally possessing at least        one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group,    -   (iv) hydrocarbyl and/or heterocarbyl silane dimer in which the        silicon atoms of the hydrocarbyl and/or heterocarbyl silane        units are bonded to each other through a bridging dialkoxy        group, each silane unit optionally possessing at least one        hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,    -   (v) silane dimer possessing a mercaptosilane unit the silicon        atom of which is bonded to the silicon atom of a hydrocarbyl        and/or heterocarbyl silane unit through a bridging dialkoxy        group, each silane unit optionally possessing at least one        hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group,    -   (vi) mercaptosilane oligomer in which the silicon atoms of        adjacent mercaptosilane units are bonded to each other through a        bridging dialkoxy group, the terminal mercaptosilane units        possessing at least one hydroxyalkoxysilyl group and/or a cyclic        dialkoxysilyl group,    -   (vii) hydrocarbyl and/or heterocarbyl silane oligomer in which        the silicon atoms of adjacent hydrocarbyl and/or heterocarbyl        silane units are bonded to each other through a bridging        dialkoxy group, the terminal mercaptosilane units possessing at        least one hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl        group, and    -   (viii) silane oligomer possessing at least one mercaptosilane        unit and at least one hydrocarbyl and/or heterocarbyl silane        unit, the silicon atoms of adjacent silane units being bonded to        each other through a bridging dialkoxy group, the terminal        silane units possessing at least one hydroxyalkoxysilyl group        and/or a cyclic dialkoxysilyl group, with the provisio that,        where the composition contains one or more of (i), (iii) and        (vi), the composition additionally contains one or more of (ii),        (iv), (v), (vii) and (viii), and where the composition contains        one or more of (ii), (iv) and (vii), the composition        additionally contains one or more of (i), (iii), (v), (vi) and        (viii). In one embodiment herein, the filler is reactive with        the mercaptofunctional silane composition. In one other        embodiment herein, free flowing filler composition can further        comprise an elastomer such as any of the elastomeric resins or        organic polymers described herein and in the amounts described        herein.

In one embodiment of the foregoing free flowing filler composition,mercaptofunctional silane composition comprises at least one of:

[G¹-(SiX^(α) _(u)Z^(β) _(v)Z^(θ) _(w))_(s)]_(m)[(HS)_(r)-G²-(SiX^(α)_(u)Z^(β) _(v)Z^(θ) _(w))_(s)]_(n)  (10)

and

[[G³-(YG²)_(k)Y]_(j)G²-(SiX^(α) _(u)Z^(β) _(v)Z^(θ)_(w))_(s)]_(m)[(HS)_(r)-G²-(SiX^(α) _(u)Z^(β) _(v)Z^(θ)_(w))_(s)]_(n)  (11)

wherein:

each occurrence of Y is independently selected from a polyvalent species(-Q)_(a)[C(=E)]_(b)(A-)_(c), wherein the atom (E) is attached to anunsaturated carbon atom;

each occurrence of G¹ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G¹ can have from 1 to about30 carbon atoms; each occurrence of G² is independently selected fromthe group consisting of divalent or polyvalent group derived bysubstitution of alkyl, alkenyl, aryl, or aralkyl wherein G² can havefrom 1 to 30 carbon atoms;

each occurrence of G³ is independently selected from the groupconsisting of monovalent and polyvalent groups derived by substitutionof alkyl, alkenyl, aryl, or aralkyl wherein G³ can have from 1 to about30 carbon atoms, with the proviso that if G³ is monovalent, G³ can behydrogen;

each occurrence of X^(α) is independently selected from the groupconsisting of —Cl, —Br, RO—, RC(═O)O—, R₂C═NO—, R₂NO—, R₂N—, —R,(HO)_(d-1)G⁴O—, HO(CR⁰ ₂)_(f)O—, and HO(CR⁰ ₂CR⁰ ₂O)_(e)— wherein each Ris independently selected from the group consisting of hydrogen,straight, cyclic or branched alkyl that can or can not containunsaturation, alkenyl groups, aryl groups, and aralkyl groups, whereineach R, other than hydrogen, contains from 1 to 18 carbon atoms, G⁴ isindependently a substituted hydrocarbon group of from about 2 to about15 carbon atoms or a substituted heterocarbon group of from about 4 to15 carbon atoms and contains one or more etheric oxygen atoms, R⁰ isindependently given by one of the members listed for R, f is from about2 to about 15, and e is from about 2 to about 7;

each occurrence of Q is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when Q issulfur, b is 0;

each occurrence of A is independently selected from the group consistingof oxygen, sulfur, and (—NR—) and with the proviso that when A issulfur, b is 0;

each occurrence of E is independently selected from the group consistingof oxygen, sulfur, and (—NR—);

each occurrence of Z^(β), which forms a bridging structure between twosilicon atoms, is independently selected from the group consisting of,[—OG⁴(OH)_(d-2)O-]_(0.5), [—O(CR⁰ ₂CR⁰ ₂O)_(e)—]_(0.5) and[—O(R⁰CR⁰)_(f)O—]_(0.5), wherein each occurrence of R⁰ is independentlygiven by one of the members listed above for R; and, each occurrence ofG⁴ is independently selected form the group consisting of a substitutedhydrocarbon group from 2 to 15 carbon atoms or a substituted hetercarbonfrom 4 to 15 carbon atoms and contain one or more etheric oxygen atoms;

each occurrence of Z^(θ), which forms a cyclic structure with a siliconatom, is independently given by —OG⁴(OH)_(d-2)O—, —O(CR⁰ ₂CR⁰ ₂O)_(e)—and —O(R⁰CR⁰)_(f)O— wherein

each occurrence of R⁰ is independently given by one of the memberslisted above for R;

each occurrence of the subscripts, a, b, c, d, e, f, j, k, m, n, r, s,u, v, and w are integers independently given by a is specifically 0 or1, and more specifically 1; b is specifically 0 or 1, and morespecifically 0; c is specifically 0 or 1, and more specifically 0; d isspecifically from about 2 to about 8, more specifically from about 2 toabout 4 and most specifically about 2; e is specifically from about 2 toabout 7, more specifically from about 2 to about 4 and most specificallyabout 2; f is specifically from about 2 to about 15, more specificallyfrom about 2 to about 4 and most specifically about 3; j is specificallyfrom 1 to about 3, more specifically from about 1 to about 2, and mostspecifically about 1; k is specifically from 0 to about 15, morespecifically from about 0 to about 5, and most specifically from about 0to about 2; m is specifically from about 1 to about 20, morespecifically from about 1 to about 5 and most specifically from about 2to 4; n is specifically from about 1 to about 20, more specifically fromabout 1 to about 5 and most specifically from about 2 to about 4; r isspecifically from 1 to about 3, and more specifically about 1; and s isspecifically from 1 to about 3, more specifically about 1; u isspecifically from 0 to 3, more specifically from about 0 to about 2, andmost specifically from about 0 to about 1; v is specifically from 0 to3, more specifically from about 0 to about 2, and most specifically fromabout 0 to about 1; w is specifically from 0 to about 1, and morespecifically about 1; with the proviso that u+v+2w=3; and with theproviso that the each of the above structures (10) and/or (11) containsat least one hydrolysable group, Z^(β) or Z^(θ). In one embodiment, itis understood that the structure, [—OG⁴(OH)_(d-2)O—]_(0.5) can furtherreact with a third or more silyl groups to form bridging trialkoxysilyl,tetraalkoxysilyl groups and so on, and are represented by[—OG⁴(OH)_(d-3)(O—)₂]_(1/3), [—OG⁴(OH)_(d-4)(O—)₃]_(1/4) and so on,respectively.

In another embodiment herein there is provided an article ofmanufacture, such as the non-limiting examples selected from the groupconsisting of tires, industrial goods, shoe soles, hoses, seals,gaskets, and cable jackets, of which at least one component is the curedrubber composition of the herein described rubber compositions. In oneembodiment, the silanes and/or silane mixtures herein offer a means forsignificantly reducing volatile organic compound (VOC) emissions duringrubber manufacture, increase the dispersion of the filler within therubber, and improving the coupling between the organic polymers andfillers.

In another embodiment herein the organofunctional silane-basedcompositions described herein are useful as coupling agents betweenelastomeric resins (i.e., rubbers) and fillers. In one embodiment, theorganofunctional silane compositions are unique in that the highefficiency of the mercaptan group can be utilized without thedetrimental side effects typically associated with the use ofmercaptosilanes, such as high processing viscosity, less than desirablefiller dispersion, premature curing (scorch), and odor. In yet anotherembodiment, these benefits are obtained because the mercaptan group ispart of a high boiling compound that liberates diol or higherpolyhydroxy-containing compound upon use. In yet still anotherembodiment, the combination of mercapto and hydrocarbyl and/orheterocarbyl groups in this silane-based composition allow for acontrolled amount filler dispersion during the preparation of the freeflowing filler composition and of coupling to the organic polymer duringthe compounding of the rubber. In yet still even another embodiment,during this non-productive mixing step, the cyclic and/or bridgedalkoxysilyl groups can react with the filler. In one embodiment hereinmercaptosilane composition, free-flowing filler composition and rubbercomposition can be cured as described herein and/or using proceduresknown to those skilled in the art.

In another specific embodiment herein, the mercaptofunctionalsilane-based compositions herein provide significant advantages overtraditional coupling agents that have found extensive use in the rubberand tire industries. These traditional silanes usually contain in theirmolecular structures three alkoxy groups, e.g., ethoxy groups, on eachsilicon atom, which results in the release of up to three moles ofsimple monohydroxy alcohol, e.g., ethanol for each silane equivalentduring the rubber manufacturing process in which the silane couples tothe filler. The release of simple mono alcohols is a great disadvantagebecause they are flammable and therefore pose a threat of fire, andbecause they contribute so greatly to volatile organic compound (VOC)emissions and are therefore potentially harmful to the environment.

In one specific embodiment herein, utilizing any of the silanes and/orsilane mixtures disclosed herein can result in VOC emission that isreduced. In one embodiment, VOC emission from a product/compositioncomprising the silanes or silanes mixtures disclosed herein can be lessthan the VOC emission in an equivalent product/composition that does notcontain said silanes or silanes mixtures disclosed herein. In yet afurther embodiment, reduced VOC emission can comprise specifically lessthan about 30 weight percent of the weight of the mercaptofunctionalsilane, more specifically less than about 10 weight percent of themercaptofunctional silane and most specifically less than about 1 weightpercent of the mercaptofunctional silane. In one embodiment, a VOCemission is defined as at least one selected from the group consistingof X^(α)—H, G(OH)_(d), (HO)(CR⁰ ₂)_(f)OH and HO(CR⁰ ₂CR⁰ ₂O)_(e)OH, allhaving a boiling point greater than 180° C. at atmospheric pressure.

In one embodiment herein, the organofunctional silane-based compositionsdescribed herein eliminate or greatly mitigate the foregoing problems byreducing volatile mono alcohol emissions to only one, less than one, andeven essentially zero, moles of mono alcohol per silane equivalent. Inone specific embodiment, they accomplish this because the silane alkoxygroups are replaced with polyhydroxy alcohols, e.g., diol derivedbridging groups, and thus such polyhydroxy alcohols are released duringthe rubber manufacture process in place of much, or nearly all, of themono alcohol released. In yet a further specific embodiment, describingthe advantages of the organofunctional silanes herein with specificreference to those silanes that are prepared with diols (such advantagesbeing realizable with polyhydroxy-containing compounds of higherhydroxyl functionality), e.g., having boiling points in excess of rubberprocessing temperatures, are not vaporized out of the rubber during therubber manufacture process, as is the case, e.g., with ethanol, but areretained by the rubber where they migrate to the silica surface due totheir high polarity and become hydrogen bonded to the surfaces ofsiliceous fillers such as silicas. In another embodiment, the presenceof diols on silica surfaces leads to further advantages not obtainablewith ethanol (due to its volatility and ejection during the rubbercompounding process) in the subsequent cure process, in which suchpresence prevents the silica surface from binding the curatives andthereby interfering with the cure. Traditional silanes not based ondiols require more curatives to counter losses due to silica binding.

In another embodiment, the addition of hydrocarbon-based diols orpolyhydroxyl-containing compounds to the rubber compounding formulationprior to and/or concurrent with the addition of curatives is ofadvantage for the efficient utilization of the curatives, in particular,and polar substances, such as, but not limited to, amines, amides,sulfenamides, thiurams, and guanidines. In yet another embodiment,whether diols or the polyhydroxyl-containing compounds are exclusivelyadded in the form of di- or polyhydroxyl-derived silanes or as freediols or polyhydroxyl-containing compounds in combination with thesilane coupling agents, the polarity of the diols orpolyhydroxyl-containing compounds is of advantage to the rubbercompounding process. In one more embodiment, these polar substances tendto migrate to the filler surface due to dipole interactions with thefiller; which tends to make them unavailable within the organic polymermatrix, where their functions include dispersion of the free flowingfiller composition and acceleration, or retardation, of the curingreactions. In one embodiment, the hydrocarbon-based diols orpolyhydroxyl-containing compounds enhance the function of the curativesby interfering with their tendency to bind to the silica surface therebyforcing them into the rubber matrix to perform their function. Inanother embodiment herein, the hydrocarbon-based diols orpolyhydroxyl-containing compounds accomplish this by themselves beingvery polar, and thereby by themselves binding to the filler surface,leaving less room for the curatives to bind to filler. In a furtherspecific embodiment, the hydrocarbon-based diols thus act as curativedisplacing agents from the filler. In yet another specific embodiment,the short chain of the hydrocarbon-based diols orpolyhydroxyl-containing compounds further enhances their function by achelate effect. In one embodiment, the number of carbon atoms betweenthe dialkoxide groups of Z^(θ) and/or Z^(β) herein are important and aredefined by the divalent radical —O(R⁰CR)_(f)O— and[—O(R⁰CR⁰)_(f)O—]_(0.5), respectively, wherein each occurrence of f is 2or 3. In a more specific embodiment, these chains of two or three carbonatoms between the two OH groups of the diol promote the formation of 5-or 6-membered rings when both oxygen atoms bind to a common silicon atomof the silanes of Formulae (10) and (11). In an even more specificembodiment, this dual binding to a common center, known, and referred toherein as the chelate effect, increases the amount of cyclicdialkoxysilyl group and inhibits the formation of gel. In a furtherspecific embodiment, after reactions with the silica in therubber-compounding step, the diols that have been released have a highaffinity to the filler because they can chelate with the metal orsilicon atom on the filler surface thereby enhancing their ability toprevent the binding of the curatives to the filler. In a furtherspecific embodiment an important advantage of the silanes and/or silanemixtures described herein is that the by-products of the silane couplingprocess are themselves of utility in enhancing the rubber compoundingprocess, the value of the resulting rubber compositions, and/or anyarticles of manufacture employing the rubber compositions. In oneembodiment, thus, the hydrocarbyl and/or heterocarbyl groups of thesilanes and/or silane mixtures (“silanes”) not only retards coupling ofsilane to polymer during mixing but also assists in the dispersion ofthe filler into the polymer during mixing by reducing the ability of thesurface hydroxyl or metal oxides to form hydrogen bonds between fillerparticles, thereby enhancing the ease and completeness of fillerdispersion and retarding the reversal of this process, namely, fillerreagglomeration.

In one embodiment herein there is provided a rubber compositioncomprising (a) at least one rubber component, (b) at least oneparticulate filler and (c) at least one mercaptofunctional silane ormercaptofunctional silane composition as described herein. In oneembodiment herein rubber composition can have any of the embodimentsdiscussed herein for free-flowing filler composition, mercaptosilanecomposition and process of making mercaptosilane and vice-versa.

In one embodiment, an important advantage of the silanes describedherein is that the by-products of the silane coupling process arethemselves of utility in enhancing the rubber compounding process, thevalue of the resulting rubber compositions, and/or any articles ofmanufacture employing the rubber compositions. In another embodiment,thus, the hydrocarbyl and/or heterocarbyl groups of the silanes hereinnot only retards coupling of silane(s) to polymer during mixing but alsoassists in the dispersion of the filler into the polymer during mixingby reducing the ability of the surface hydroxyl or metal oxides to formhydrogen bonds between filler particles, thereby enhancing the ease andcompleteness of filler dispersion and retarding the reversal of thisprocess, namely, filler reagglomeration.

In one embodiment, at least one of the organofunctional silane couplingagents that contain cyclic and/or bridging dialkoxysilyl groups andmercapto and hydrocarbyl and/or heterocarbyl groups is mixed with theorganic polymer before, during, or after the compounding of the fillerinto the organic polymer. In one embodiment, the silanes are addedbefore or during the compounding of the filler into the organic polymerbecause these silanes facilitate and improve the dispersion of thefiller. In a more specific embodiment, the total amount of silanepresent in the resulting rubber composition should be about 0.05 toabout 25 parts by weight per hundred parts by weight of organic polymer(phr). In another embodiment, the amount of mercaptofunctional silanepresent in the free flowing filler composition is from about 0.1 toabout 70 weight percent based on total weight of free flowing fillercomposition. In yet another embodiment, the amount of mercaptofunctionalsilane present in the free flowing filler composition is from about 0.5to about 20 weight percent based on total weight of free flowing fillercomposition. In one other embodiment the amount of filler in the freeflowing filler composition is from about 99.9 to about 30 weight percentbased on total weight of free flowing filler composition. In yet oneother embodiment the amount of filler in the free flowing fillercomposition is from about 99.5 to about 80 weight percent based on totalweight of free flowing filler composition. In another embodiment, theamount of silane present in the rubber is from about 1 to 10 phr. In yetanother embodiment, the amount of silane present in the rubber is fromabout 3 to 8 phr. In one embodiment, fillers can be used in quantitiesranging specifically from about 5 to about 100 phr, more specificallyfrom about 25 to about 80 phr and most specifically from about 50 toabout 70 phr.

In one embodiment, in practice, sulfur vulcanized rubber productstypically are prepared by thermomechanically mixing rubber and variousingredients in a sequentially step-wise manner followed by shaping andcuring the compounded rubber to form a vulcanized product. In a morespecific embodiment, first, for the aforesaid mixing of the rubber andvarious ingredients, typically exclusive of sulfur and sulfurvulcanization accelerators (collectively “curing agents”), the rubber(s)and various rubber compounding ingredients are usually blended in atleast one, and optionally (in the case of silica filled low rollingresistance tires) two or more, preparatory thermomechanical mixingstage(s) in suitable mixers. In a further embodiment, such preparatorymixing is referred to as non-productive mixing or non-productive mixingsteps or stages. In a more specific embodiment, such preparatory mixingusually is conducted at temperatures in the range of from about 140° C.to about 200° C. and often in the range of from about 150° C. to about180° C.

In one embodiment, subsequent to such preparatory mix stages, in a finalmixing stage, sometimes referred to as a productive mix stage, curingagents, and possibly one or more additional ingredients, are mixed withthe rubber compound or composition, typically at a temperature in arange of 50° C. to 130° C., which is a lower temperature than thoseutilized in the preparatory mix stages to prevent or retard prematurecuring of the sulfur curable rubber, which is sometimes referred to asscorching of the rubber composition.

In another embodiment, the rubber mixture, sometimes referred to as arubber compound or composition, typically is allowed to cool, sometimesafter or during a process of intermediate mill mixing, between theaforesaid various mixing steps, for example, to a temperature of about50° C. or lower.

In another embodiment herein, when it is desired to mold and to cure therubber, the rubber is placed into the appropriate mold and heated toabout at least 130° C. and up to about 200° C., which will cause thevulcanization of the rubber by the mercapto groups on the mercaptosilaneand any other free sulfur sources in the rubber mixture.

In one embodiment, by thermomechanical mixing, it is meant that therubber compound, or composition of rubber and rubber compoundingingredients, is mixed in a rubber mixture under high shear conditionswhere it autogenously heats up as a result of the mixing, primarily dueto shear and associated friction within the rubber mixture in the rubbermixer. In one embodiment, several chemical reactions can occur atvarious steps in the mixing and curing processes.

In one embodiment, the first reaction is a relatively fast reaction andis considered herein to take place between the filler and thealkoxysilyl group of the cyclic and/or bridging dialkoxy blockedmercaptofunctional silanes, —SiX^(α) _(u)Z^(β) _(v)Z^(θ) _(w), herein.In a further embodiment, such reaction can occur at a relatively lowtemperature, such as, for example, about 120° C. In a furtherembodiment, the second reaction is considered herein to be the reactionwhich takes place between the sulfur-containing portion of the silane,and the sulfur vulcanizable rubber at a higher temperature; for example,above about 140° C.

In one embodiment, another sulfur source can be used, for example, inthe form of elemental sulfur as S₈. In a more specific embodiment, asulfur donor is considered herein as a sulfur-containing compound thatliberates free, or elemental sulfur, at a temperature in a range ofabout 140° C. to about 190° C. In an even more specific embodiment, suchsulfur donors can be those such as the non-limiting examples ofpolysulfide vulcanization accelerators with at least two connectingsulfur atoms in their polysulfide bridge. In an even yet more specificembodiment, the amount of free sulfur source addition to the mixture canbe controlled or manipulated as a matter of choice relativelyindependently from the addition of the aforesaid cyclic and/or bridgingdialkoxy mercaptofunctional silane composition.

Thus, in one embodiment for example, the independent addition of asulfur source can be manipulated by the amount of addition thereof andby sequence of addition relative to addition of other ingredients to therubber mixture.

In another embodiment herein, a rubber composition is prepared by aprocess comprising the sequential steps of:

-   -   (a) thermomechanically mixing, in at least one preparatory        mixing step, to a temperature of 140° C. to 200° C.,        alternatively to 140° C. to 180° C., for a total mixing time of        2 to 20, alternatively 4 to 15, minutes for such mixing step(s):        -   i) 100 parts by weight of at least one sulfur vulcanizable            rubber selected from conjugated diene homopolymers and            copolymers, and copolymers of at least one conjugated diene            and aromatic vinyl compound,        -   ii) 5 to 100, preferably 25 to 80, phr of particulate            filler, wherein the filler preferably contains from 1 to 85            weight percent carbon black, and        -   iii) 0.05 to 20 parts by weight filler of at least one            mercaptofunctional cyclic and/or bridging dialkoxy silane of            the composition described herein;    -   (b) subsequently blending therewith, in a final thermomechanical        mixing step at a temperature to 50° C. to 130° C. for a time        sufficient to blend the rubber, specifically between 1 to 30        minutes, more specifically 1 to 3 minutes, and a curing agent at        0 to 5 phr; and, optionally; and,    -   (c) curing said mixture at a temperature in the range of from        130 to 200° C. for about 5 to 60 minutes.

In one embodiment, suitable rubber component (a) (organic polymers) andfillers are well known in the art and are described in numerous texts,of which two examples include The Vanderbilt Rubber Handbook; R. F. Ohm,ed.; R. T. Vanderbilt Company, Inc., Norwalk, Conn.; 1990 and Manual ForThe Rubber Industry; T. Kempermann, S. Koch, J. Sumner, eds.; Bayer AG,Leverkusen, Germany; 1993. In yet an even further embodiment, somerepresentative non-limiting examples of suitable rubber component (a)(organic polymers) include solution styrene-butadiene rubber (SSBR),emulsion styrene-butadiene rubber (ESBR), natural rubber (NR),polybutadiene (BR), ethylene-propylene ter-polymers (EPDM), andacrylonitrile-butadiene rubber (NBR).

In another embodiment herein, the rubber composition component (a) iscomprised of at least one diene-based elastomer, or rubber. In an evenmore specific embodiment, suitable monomers for preparing the rubbersare conjugated dienes which are those such as the non-limiting examplesof isoprene and 1,3-butadiene; and suitable vinyl aromatic compoundswhich are those such as the non-limiting examples of styrene and alphamethyl styrene; and combinations thereof. Thus in a more specificembodiment, the rubber is a sulfur curable rubber. In a furtherembodiment, such diene based elastomer, or rubber, can be selected, fromthe non-limiting examples of at least one of cis-1,4-polyisoprene rubber(natural and/or synthetic), and preferably natural rubber), emulsionpolymerization prepared styrene/butadiene copolymer rubber, organicsolution polymerization prepared styrene/butadiene rubber,3,4-polyisoprene rubber, isoprene/butadiene rubber,styrene/isoprene/butadiene terpolymer rubber, cis-1,4-polybutadiene,medium vinyl polybutadiene rubber (35-50 percent vinyl), high vinylpolybutadiene rubber (50-75 percent vinyl), styrene/isoprene copolymers,emulsion polymerization prepared styrene/butadiene/acrylonitrileterpolymer rubber and butadiene/acrylonitrile copolymer rubber. Anemulsion polymerization derived styrene/butadiene (ESBR) is alsocontemplated as diene based rubbers for use herein such as those havinga relatively conventional styrene content of 20 to 28 percent boundstyrene or, for some applications, an ESBR having a medium to relativelyhigh bound styrene content, namely, a bound styrene content of 30 to 45percent. In an even further specific embodiment, emulsion polymerizationprepared styrene/butadiene/acrylonitrile terpolymer rubbers containing 2to 40 weight percent bound acrylonitrile in the terpolymer are alsocontemplated as diene based rubbers for use herein.

In another embodiment herein, the solution polymerization prepared SBR(SSBR) typically has a bound styrene content in a range of specificallyfrom about 5 to about 50, more specifically from about 9 to about 36,and most specifically of from about 20 to about 30 weight percent. In amore specific embodiment, polybutadiene elastomer can he convenientlycharacterized, for example, by having at least a 90 weight percentcis-1,4-content.

In one embodiment some representative non-limiting examples of suitablefiller materials include include metal oxides, such as silica (pyrogenicand precipitated), titanium dioxide, aluminosilicate, and alumina,siliceous materials, including clays and talc, and carbon black. In amore specific embodiment, particulate, precipitated silica is alsosometimes used for such purpose, particularly in connection with asilane. In one embodiment wherein the filler is a silica alone or incombination with one or more other fillers. In another specificembodiment in some cases, a combination of silica and carbon black isutilized for reinforcing fillers for various rubber products, includingtreads for tires. In one embodiment, alumina can be used either alone orin combination with silica. The term “alumina” can be described hereinas aluminum oxide, or Al₂O₃. In a further specific embodiment, thefillers can be hydrated or in anhydrous form. Use of alumina in rubbercompositions is known, see, for example, U.S. Pat. No. 5,116,886 and EP631 982, the contents of which are incorporated by reference herein.

In one embodiment there is provided herein a process for preparing arubber composition comprising adding to a rubber compositionreaction-forming mixture, such as a mixture of the herein describedrubber composition components (a), (b) and (c) in an effective amount ofat least one mercaptofunctional silane composition as described herein.In one embodiment an effective amount of mercaptofunctional silanecomposition, in a rubber composition reaction forming mixture, asdescribed herein, is specifically of from about 1 to about 20, morespecifically of from about 3 to about 15 and most specifically of fromabout 5 to about 10 weight percent of mercaptofunctional silane based onthe total weight of rubber composition reaction forming mixture. Inanother embodiment, reaction-forming mixture further comprises a filleras described herein and in an amount of specifically of from about 2 toabout 70, more specifically of from about 5 to about 50 and mostspecifically of from about 20 to about 40 weight percent of filler,based on the total weight of rubber composition reaction-formingmixture. In yet another embodiment reaction-forming mixture can evenfurther comprise a rubber component (a) described herein, and in anamount of specifically of from about 30 to about 98, more specificallyof from about 50 to about 95 and most specifically of from about 60 toabout 80 weight percent of rubber component based on the total weight ofrubber composition reaction forming mixture. In one embodiment herein,rubber composition as described herein can have amounts of components(a), (b) and (c) as described for rubber component reaction formingmixture.

In one embodiment, the organofunctional silane compositions that containcyclic and/or bridging dialkoxysilyl groups and mercapto andheterocarbyl and/or hydrocarbyl groups can be premixed, or pre-reacted,with the filler particles or added to the rubber mix during the rubberand filler processing, or mixing stage. In another embodiment, if thesilane and filler are added separately to the rubber mix during therubber and filler mixing, or processing stage, it is considered that theorganofunctional silane compositions that contain cyclic and/or bridgingdialkoxysilyl groups and mercapto and heterocarbyl and/or hydrocarbylgroups then couple in situ to the filler.

In one embodiment herein, vulcanized rubber composition should contain asufficient amount of filler to contribute a reasonably high modulus andhigh resistance to tear. In a specific embodiment, the combined weightof the filler can be as low as about 5 to about 100 phr, but is morespecifically of from about 25 to about 85 phr, and most specifically offrom about 50 to about 70 phr.

In one embodiment the term “filler” as used herein means a substancethat is added to the elastomer to either extend the elastomer or toreinforce the elastomeric network. Reinforcing fillers are materialswhose moduli are higher than the organic polymer of the elastomericcomposition and are capable of absorbing stress from the organic polymerwhen the elastomer is strained. In one embodiment fillers includedfibers, particulates, and sheet-like structures and can be composed ofinorganic minerals, silicates, silica, clays, ceramics, carbon, organicpolymers, diatomaceous earth. In one embodiment the filler herein can beessentially inert to the silane with which it is admixed, or it can bereactive therewith.

In one embodiment the term “particulate filler” as used herein means aparticle or grouping of particles to form aggregates or agglomerates. Inone embodiment the particulate filler herein can be essentially inert tothe silane with which it is admixed, or it can be reactive therewith.

In one embodiment the term “carrier” as used herein means a porous orhigh surface area filler that has a high adsorption or absorptioncapability and is capable of carrying up to 75 percent liquid silanewhile maintaining its free-flowing and dry properties. In one embodimentthe carrier filler herein is essentially inert to the silane and iscapable of releasing or deabsorbing the liquid silane when added to theelastomeric composition.

In an embodiment, fillers of the present invention can be used ascarriers for liquid silanes and reinforcing fillers for elastomers inwhich the mercapto functional silane, and more specifically, themercaptofunctional silane (10) or (11) is capable of reacting or bondingwith the surface. In one embodiment, the fillers that are used ascarrier should be non-reactive with the with the mercaptosilane of thisinvention. In one embodiment the non-reactive nature of the fillers isdemonstrated by ability of the merpcaptosilane to be extracted atgreater than 50 percent of the loaded silane using an organic solvent.In one embodiment the extraction procedure is given in U.S. Pat. No.6,005,027, which is incorporated herein by reference. In one embodiment,carriers include, but are not limited to, porous organic polymers,carbon black, diatomaceous earth, and silicas that characterized byrelatively low differential of less than 1.3 between the infraredabsorbance at 3502 cm⁻² of the silica when taken at 105° C. and whentaken at 500° C., as described in U.S. Pat. No. 6,005,027. In oneembodiment, the amount of mercapto functional silane that can be loadedon the carrier is between 0.1 and 70 percent. In another embodiment, themercpato functional silane is load on the carrier at concentrationsbetween 10 and 50 percent. In yet another embodiment, the filler is aparticulate filler.

In one embodiment herein reinforcing fillers useful herein includefillers in which the silanes are reactive with the surface of thefiller. In one embodiment some representative examples of the fillersinclude, but are not limited to, inorganic fillers, siliceous fillers,metal oxides such as silica (pyrogenic and/or precipitated), titanium,aluminosilicate and alumina, clays and talc, and the like. In oneembodiment herein, particulate, precipitated silica is useful for suchpurpose, particularly when the silica has reactive surface silanols. Inone embodiment of the present invention, a combination of 0.1 to 20percent of mercapto functional silane, and more specifically, themercapto functional silanes (10) or (11) and 80 to 99.9 percent silicaor other reinforcing fillers is utilized to reinforce various rubberproducts, including treads for tires. In another embodiment, a filler iscomprising from about 0.5 to about 10 percent mercaptofunctional silane,and more specifically, mercapto functional silane (10) or (11) and about90 to about 99.5 weight percent particulate filler. In anotherembodiment herein, alumina can be used alone with the mercaptofunctional silane, and more specifically, mercaptofunctional silane (10)or (11) or in combination with silica and the mercapto functionalsilane. In one embodiment herein the term, alumina, can be describedherein as aluminum oxide, or Al₂O₃. In a further embodiment herein, thefillers may be in the hydrated form.

In one embodiment the filler can be essentially inert to the silane withwhich it is admixed as is the case with carbon black or organicpolymers, or it can be reactive therewith, e.g., the case with carrierspossessing metal hydroxyl surface functionality, e.g., silicas and othersiliceous particulates which possess surface silanol functionality.

In one embodiment herein, precipitated silica is utilized as filler. Ina more specific embodiment, the silica filler herein can ascharacterized by having a BET surface area, as measured using nitrogengas, specifically in the range of from about 40 to about 600 m²/g, andmore specifically in a range of from about 50 to about 300 m²/g and mostspecifically in a range of from about 100 to about 150 m²/g. In anotherspecific embodiment, the BET method of measuring surface area isdescribed in the Journal of the American Chemical Society, Volume 60,page 304 (1930), which is the method used herein. In yet anotherspecific embodiment, the silica typically can also be characterized byhaving a dibutylphthalate (DBP) absorption value in a range ofspecifically from about 100 to about 350, more specifically from about150 to about 300 and most specifically from about 200 to about 250. Inan even further specific embodiment, further, useful silica fillers, aswell as the aforesaid alumina and aluminosilicate fillers, can beexpected to have a CTAB surface area in a range of from about 100 toabout 220 m²/g. In an even further specific embodiment, the CTAB surfacearea is the external surface area as evaluated by cetyltrimethylammonium bromide with a pH of 9; the method is described inASTM D 3849.

In one embodiment, mercury porosity surface area is the specific surfacearea determined by mercury porosimetry. In this technique, mercury ispenetrated into the pores of the sample after a thermal treatment toremove volatiles. In a more specific embodiment, set-up conditions canbe suitably described as using a 100 mg sample; removing volatilesduring 2 hours at 105° C. and ambient atmospheric pressure; and ambientto 2000 bars pressure measuring range. In another more specificembodiment, such evaluation can be performed according to the methoddescribed in Winslow, et al. in ASTM bulletin, p. 39 (1959) or accordingto DIN 66133; for such an evaluation, a CARLO-ERBA Porosimeter 2000 canbe used. In one embodiment, the average mercury porosity specificsurface area for the selected silica filler should be in a range ofspecifically from about 100 to about 300 m²/g, more specifically fromabout 150 to about 275 m²/g, and most specifically from about 200 toabout 250 m²/g.

In one embodiment, a suitable pore size distribution for the silica,alumina and aluminosilicate according to such mercury porosityevaluation is considered herein to be: five percent or less of its poreshaving a diameter of less than about 10 nm; from about 60 to about 90percent of its pores have a diameter of from about 10 to about 100 nm;from 10 to about 30 percent of its pores having a diameter of from about100 to about 1,000 μm; and from about 5 to about 20 percent of its poreshave a diameter of greater than about 1,000 nm. In a second embodiment,the silica can be expected to have an average ultimate particle size,for example, in the range of from about 0.01 to about 0.05 μm asdetermined by electron microscopy, although the silica particles can beeven smaller, or possibly larger, in size. In one embodiment, variouscommercially available silicas can be considered for use herein such as,those available from PPG Industries under the HI-SIL trademark, inparticular, HI-SIL 210, and 243; silicas available from Rhone-Poulenc,e.g., ZEOSIL 1165 MP; silicas available from Degussa, e.g., VN2 and VN3,etc. and silicas available from Huber, e.g., HUBERSIL 8745.

In one embodiment, where it is desired for rubber composition, whichcontains both a siliceous filler such as silica, alumina and/oraluminosilicates and also carbon black reinforcing pigments, to beprimarily reinforced with silica as the reinforcing pigment, it is oftenmore specific that the weight ratio of such siliceous fillers to carbonblack is at least 3/1 and preferably at least 10/1 and, thus, in a rangeof 3/1 to 30/1. In a more specific embodiment, the filler can comprisefrom about 15 to about 95 weight percent precipitated silica, aluminaand/or aluminosilicate and, correspondingly from about 5 to about 85weight percent carbon black, wherein the said carbon black has a CTABvalue in a range of from about 80 to about 150. In one specificembodiment, alternatively, the filler can comprise from about 60 toabout 95 weight percent of said silica, alumina and/or aluminosilicateand, correspondingly, from about 40 to about 5 weight percent of carbonblack. In another specific embodiment, the siliceous filler and carbonblack can be pre-blended or blended together in the manufacture of thevulcanized rubber.

In one embodiment, the rubber composition herein can be compounded bymethods known in the rubber compounding art, such as mixing the varioussulfur-vulcanizable constituent rubbers with various commonly usedadditive materials as, for example, curing aids such as sulfur,activators, retarders and accelerators, processing additives such asoils, resins e.g., tackifying resins, silicas, plasticizers, fillers,pigments, fatty acid, zinc oxide, waxes, antioxidants and antiozonants,peptizing agents, and reinforcing materials such as, for example, carbonblack, and the like. In another specific embodiment, depending on theintended use of the sulfur vulcanizable and sulfur vulcanized material(rubbers), the additives mentioned herein are selected and commonly usedin conventional amounts.

In one embodiment, the vulcanization can be conducted in the presence ofan additional sulfur vulcanizing agent. In one specific embodiment, somenon-limiting examples of suitable sulfur vulcanizing agents include,e.g., elemental sulfur (free sulfur) or sulfur donating vulcanizingagents, such as the non-limiting examples of, an amino disulfide,polymeric polysulfide or sulfur olefin adducts, which are conventionallyadded in the final, productive, rubber composition mixing step. Inanother specific embodiment, the sulfur vulcanizing agents (which arecommon in the art) are used, or added in the productive mixing stage, inan amount ranging from about 0.4 to about 3 phr, or even, in somecircumstances, up to about 8 phr, with a range of from about 1.5 toabout 2.5 phr, and in some cases from about 2 to about 2.5 phr, beingmost specific.

In one embodiment, vulcanization accelerators, i.e., additional sulfurdonors, can also be used. In one embodiment, it will be appreciated thatthey can be those such as the non-limiting examples of benzothiazole,alkyl thiuram disulfide, guanidine derivatives, and thiocarbamates. Inanother specific example, representative of such accelerators are, e.g.,but not limited to, mercapto benzothiazole, tetramethyl thiuramdisulfide, benzothiazole disulfide, diphenylguanidine, zincdithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate,N-dicyclohexyl-2-benzothiazolesulfenamide,N-cyclohexyl-2-benzothiazolesulfenamide,N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphenylthiourea,dithiocarbamylsulfenamide, N,N-diisopropylbenzothiozole-2-sulfenamide,zinc-2-mercaptotoluimidazole, dithiobis(N-methyl piperazine),dithiobis(N-beta-hydroxy ethyl piperazine), dithiobis(dibenzyl amine)and combinations thereof. In another specific embodiment, otheradditional sulfur donors, include, e.g., thiuram and morpholinederivatives. In a more specific embodiment, representative of suchdonors include, e.g., but are not limited to, dimorpholine disulfide,dimorpholine tetrasulfide, tetramethyl thiuram tetrasulfide,benzothiazyl-2,N-dithiomorpholide, thioplasts, dipentamethylenethiuramhexasulfide, disulfidecaprolactam and combinations thereof.

In one embodiment, accelerators are used to control the time and/prtemperature required for vulcanization and to improve the properties ofthe vulcanizate. In one embodiment, a single accelerator system can beused, i.e., a primary accelerator. In another embodiment, conventionallyand more specifically, a primary accelerator(s) is used in total amountsranging from about 0.5 to about 4, preferably from about 0.8 to about1.5, phr. In a more specific embodiment, combinations of a primary and asecondary accelerator can be used with the secondary accelerator beingused in smaller amounts (e.g., from about 0.05 to about 3 phr) in orderto activate and to improve the properties of the vulcanizate. In yet afurther embodiment, delayed action accelerators can also be used. In yetan even further embodiment, vulcanization retarders can also be used. Inone embodiment, suitable types of accelerators are those such as thenon-limiting examples of amines, disulfides, guanidines, thioureas,thiazoles, thiurams, sulfenamides, dithiocarbamates, xanthates andcombinations thereof. In a more specific embodiment, the primaryaccelerator is a sulfenamide. In another specific embodiment, if asecond accelerator is used, the secondary accelerator is morespecifically a guanidine, dithiocarbamate or thiuram compound.

In one embodiment some non-limiting amounts of tackifier resins, ifused, can be from about 0.5 to about 10 phr, usually from about 1 toabout 5 phr. In one specific embodiment, typical amounts of processingaids comprise from about 1 to about 50 phr. In another specificembodiment, such processing aids can include, the non-limiting examplesof aromatic, naphthenic and/or paraffinic processing oils, andcombinations thereof. In one more specific embodiment, typical amountsof antioxidants are from about 1 to about 5 phr. In one other specificembodiment, representative antioxidants include, the non-limitingexamples of diphenyl-p-phenylenediamine and others, e.g., thosedisclosed in the Vanderbilt Rubber Handbook (1978), pages 344-346. Inyet another embodiment, typical amounts of antiozonants, are from about1 to about 5 phr. In one more embodiment, typical amounts of fattyacids, if used, which can include the non-limiting example of stearicacid, are from about 0.5 to about 3 phr. In one more embodiment, typicalamounts of zinc oxide are from about 2 to about 5 phr. In yet anotherspecifice embodiment, typical amounts of waxes are from about 1 to about5 phr. In one embodiment, often microcrystalline waxes are used. Inanother embodiment, typical amounts of peptizers are from about 0.1 toabout 1 phr. In yet a further embodiment, typical peptizers include, thenon-limiting examples of pentachlorothiophenol, dibenzamidodiphenyldisulfide and combinations thereof.

In one embodiment herein, rubber compositions herein can be used forvarious purposes. In one specific embodiment, for example, they can beused for the non-limiting examples of various tire compounds, shoesoles, hoses, cable jackets, gaskets, and other industrial goods. In amore specific embodiment, such articles can be built, shaped, molded andcured by various known and conventional methods as is readily apparentto those skilled in the art. In one even more specific embodiment, oneparticularly useful application of the rubber compositions herein is forthe manufacture of tire treads. In one embodiment, an advantage oftires, tire treads, or other articles of manufacture derived from therubber compositions herein is that they suffer from less VOC emissionsduring their lifetime and use as a result of having been manufacturedfrom a rubber compound that contains less residual silane ethoxy groupsthan do rubber compounds of the known and currently practiced art. In amore specific embodiment, this is a direct result of having useddialkoxy-functional silane coupling agents in their manufacture, whichcontain fewer or essentially no ethoxy groups on silicon, relative tothe blends of alkylsilane and mercaptosilane coupling agents of thecurrently known and practiced art. In one embodiment, the lack orreduction of ethoxysilane groups in the coupling agents used results infewer residual ethoxy groups on silicon after the article of manufactureis produced, from which less or no ethanol can be released by hydrolysisof the residual ethoxysilane groups by exposure of the article ofmanufacture to water during use.

All references cited herein are incorporated by reference herein intheir entirety.

The invention can be better understood by reference to the followingexamples in which the parts and percentages are by weight unlessotherwise indicated.

EXAMPLES Comparative Example 1

Into a 200 ml glass jar were charged n-octyltriethoxysilane (66.5 grams,0.241 mole) and 3-mercaptopropyltriethoxysilane (15.5 grams, 0.065 mol).The jar was purged with dry nitrogen, sealed and then shaken for 1minute to thoroughly mix the two components. The n-octyltriethoxysilaneand 3-mercaptopropyltriethoxysilane were obtained from GE AdvancedMaterials—Silicones under the trade names SILQUEST® A-137 silane andSILQUEST® A-1891 silane, respectively.

Comparative Example 2

Into a 100 ml glass jar were charged polyalkyleneoxidealkoxysilane,obtained from GE Advanced Materials—Silicones under the trade namesSILQUEST® A-1230 silane (48.7 grams) and 3-mercaptopropyltriethoxysilane(8.2 grams, 0.034 mol). The jar was purged with dry nitrogen, sealed andthen shaken for 1 minute to thoroughly mix the two components. Thepolyalkyleneoxidealkoxysilane and 3-mercaptopropyltriethoxysilane wereobtained from GE Advanced Materials—Silicones under the trade namesSILQUEST® A-1230 silane and SILQUEST® A-1891 silane, respectively.

Example 3

n-Octyltriethoxysilane (219 grams, 0.792 mole) and3-mercaptopropyltriethoxysilane (81 grams, 0.34 mole) were added to a500 ml round-bottomed flask equipped with a magnetic stirrer, short pathcondenser and receiver flask. Sulfuric acid (0.3 g) was added to thereaction flask and the mixture was heated to 50° C. under a vacuum of 50torr. 2-Methylpropane-1,3-diol (306 grams, 3.395 moles) was added viaaddition funnel. Ethanol (155 grams, 3.37 moles) was collected. A 21%ethanolic solution of sodium ethoxide (1.45 g) was added to neutralizethe catalyst.

Example 4

3-Mercaptopropyltriethoxysilane (272 grams, 1.143 moles) was added to a500 ml round-bottomed flask equipped with a magnetic stirrer, short pathcondenser and receiver flask. Sulfuric acid (0.19 g) was added to thereaction flask and the mixture was heated to 50° C. under a vacuum of 50torr. 2-Methylpropane-1,3-diol (308 grams, 3.42 moles) was added viaaddition funnel. Ethanol (152 g) was collected. A 21% ethanolic solutionof sodium ethoxide (0.72 g) was added to neutralize the catalyst.

Example 5

Polyalkyleneoxidealkoxysilane, obtained from GE AdvancedMaterials—Silicones under the trade names SILQUEST® A-1230 silane, (557grams) was added to a round-bottomed flask equipped with a magneticstirrer, short path condenser and receiver flask. Sulfuric acid (0.41 g)was added to the reaction flask and the mixture was heated to 50° C.under a vacuum of 50 torr. 2-Methylpropane-1,3-diol (287 grams, 3.18moles) was added via addition funnel. Methanol (58 grams, 1.8 moles) wascollected. A 21% ethanolic solution of sodium ethoxide (1.35 g) wasadded to neutralize the catalyst.

Example 6

Into a 100 ml glass jar were charged the silane from Example 4 (62.9grams) and silane from Example 5 (19.7 grams). The jar was purged withdry nitrogen, sealed and then shaken for 1 minute to thoroughly mix thetwo components.

Example 7

Polyalkyleneoxidealkoxysilane, obtained from GE AdvancedMaterials—Silicones under the trade names SILQUEST® A-1230 silane, (746grams) and 3-mercaptopropyltrimethoxysilane (157 grams, 0.80 moles) wereadded to a round-bottomed flask equipped with a magnetic stirrer, shortpath condenser and receiver flask. Sulfuric acid (0.76 g) was added tothe reaction flask and the mixture was heated to 50° C. under a vacuumof 50 torr. 2-Methylpropane-1,3-diol (594 grams, 6.59 moles) was addedvia addition funnel. Methanol (157 grams) was collected. A 21% ethanolicsolution of sodium ethoxide (1.45 g) was added to neutralize thecatalyst.

Comparative Examples 8 and 9, Examples 10 and 11

Cured rubber compositions in the form of plaques (Comparative Examples 8and 9 employing the silanes of Comparative Examples 1 and 2,respectively, and Examples 10 and 11 employing the silanes of Examples 3and 6, respectively) were prepared and their physical and dynamicproperties measured.

A typical silica-rubber SBR formulation was used as described below inTable 1. Mixing was carried out in a 1550 ml Krupp intermeshing mixer.The silane loadings were 8.2 phr.

TABLE 1 Silica-Silane/Rubber Formulation PHR Components 103.2 sSBR (BunaVSL 5525-1) - (Bayer AG) 25 BR (Budene 1207) - (Goodyear) 80 silica -Zeosil 1165MP, (Rhodia) 8.2 Silane 4.5 oil - Sundex 8125 (Sun Oil) 2.5zinc oxide - Kadox 720C (ZincCorp.) 1.0 stearic acid - Industrene R(Witco, Crompton) 2.0 6 PPD - Flexzone 7P (Uniroyal, Crompton) 1.5 Wax -Sunproof Improved (Uniroyal, Crompton) Final Mix Ingredients 1.4Rubbermakers Sulfur 104, Harwick 1.7 CBS - Delac S (Uniroyal, Crompton)2.0 DPG - (Uniroyal, Crompton)

The procedure which was used for preparing a single non-productive mixis presented in Table 2 below.

TABLE 2 One Pass Procedure; Cooling with water @ 25° C., 68% fillfactor: Step Procedure 1 Add polymers, RDM (ram down mix) 60 seconds 2Add 50% silica, all silane, oil, RDM 60 seconds 3 Add remaining 50%silica, wax, RDM 90 seconds 4 Dust down, RDM 30 seconds 5 Add remainderof ingredients, RDM 60 seconds 6 Dust down, RDM to 160–170° C. (inapprox. 2 minutes) by increasing rotor speed 7 Hold at 170° C. (orhigher temperature) for 8 minutes by changing speeds on the mixer. 8Dump, sheet off roll mill @ 65–70° C. to cool

The procedure for preparing a single productive mix involved addingsulfur and accelerators (primary and secondary) into a masterbatchprepared as described in Table 2 on a two-roll mill at 65 to 70° C.After all the silica filler, silane and oil were incorporated into agiven mix, the rpm of the rotors was raised so as to achieve the desiredsilanization temperature. The mix was then held at that temperature for8 minutes. The mix procedures are shown in Table 2, above.

Curing and testing of the cured rubber compositions in the form ofplaques were carried out according to ASTM standards. In addition, smallstrain dynamic tests were carried out on a Rheometrics Dynamic Analyzer(ARES—Rheometrics Inc.). The specific curing procedure, measurements andmeasuring procedures were as follows:

Curing Procedure/Measurement Testing Standard Mooney viscosity andscorch ASTM D1646 Oscillating disc rheometry ASTM D2084 Curing of testplaques ASTM D3182 Stress-strain properties ASTM D412 Heat build-up ASTMD623

Dynamic Mechanical Properties:

Payne effect strain sweeps were carried out from dynamic strainamplitudes of 0.01% to about 25% shear strain amplitude at 10 Hz and 60°C. The dynamic parameters, G′_(initial), ΔG′, G″_(max), tan δ_(max) wereextracted from the non-linear responses of the rubber compounds at smallstrains. In some cases, steady state values of tan δ were measured after15 minutes of dynamic oscillations at strain amplitudes of 35% (at 60°C.). Temperature dependence of dynamic properties were also measuredfrom about −80° C. to +80° C. at small strain amplitudes (1 or 2%) at afrequency of 10 Hz. The Theological, physical and dynamic properties ofthe rubber compounds, Comparative Examples 8 and 9 and Example 10 and 11are given in Table 3.

TABLE 3 The rheological, physical and dynamic properties of filledelastomers made with silanes herein. Example Number 8 9 10 11 MooneyViscosity @100° C. ML1 + 4 61 100.97 55.86 70.39 Mooney Scorch @135° C.M_(V) 32.12 54.05 28.07 34.21 MS1+, t₃, minutes 9.01 9.01 9.29 7.44MS1+, t₁₈, minutes 12.54 11.02 11.37 10.58 Oscillating Disc Rheometer @149° C., 1° arc, 30 minute timer M_(L), dNm 8.19 14.69 7.51 10.20 M_(H),dNm 28.3 40.35 28.54 32.05 M_(H) − M_(L) 20.11 25.66 21.03 21.85 t_(s1),minutes 5.43 2.68 5.67 4.35 t90, minutes 21.89 16.12 9.86 10.91 PhysicalProperties, cured t90 @ 149° C. Hardness, Shore A 47.3 56.7 52 54.0Elongation, % 428 379 416 432 25% Modulus, MPa 0.64 0.89 0.77 0.82 100%Modulus, MPa 1.58 2.2 2.04 1.9 300% Modulus, MPa 10.23 14.6 12.74 12.7Tensile, MPa 18.78 20.8 20.55 22.4 RI 300/25 16.01 16.43 16.50 15.42 RI300/100 6.49 6.55 6.26 6.58 DIN Abrasion mm³ loss 96 122 DynamicProperties in the Cured State Non-linearity (0–10%) @ 60° C.G′_(initial) (MPa) 2.39 1.89 ΔG′ (MPa) 1.17 0.75 G″_(max) (MPa) 0.280.19 tanδ_(max) 0.14 0.12 Low Temperature Viscoelasticity tan δ0° C.0.34 0.42 tan δ60° C. 0.13 0.12

While the invention has been described with reference to a number ofexemplary embodiments, it will be understood by those skilled in the artthat various changes can be made and equivalents can be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications can be made to adapt a particular situationor material to the teachings of the invention without departing fromessential scope thereof. Therefore, it is intended that the inventionnot be limited to any particular exemplary embodiment disclosed herein.

1. A rubber composition comprising: (a) at least one rubber component,(b) at least one particulate filler and (c) at least onemercaptofunctional silane composition comprising at least oneorganofunctional silane selected from the group consisting of: (i)mercaptosilane possessing at least one hydroxyalkoxysilyl group and/or acyclic dialkoxysilyl group, (ii) hydrocarbyl and/or heterocarbyl silanepossessing at least one hydroxyalkoxysilyl group and/or a cyclicdialkoxysilyl group, (iii) mercaptosilane dimer in which the siliconatoms of the mercaptosilane units are bonded to each other through abridging dialkoxy group, each silane unit optionally possessing at leastone hydroxyalkoxysilyl group and/or a cyclic dialkoxysilyl group, (iv)hydrocarbyl and/or heterocarbyl silane dimer in which the silicon atomsof the hydrocarbyl and/or heterocarbyl silane units are bonded to eachother through a bridging dialkoxy group, each silane unit optionallypossessing at least one hydroxyalkoxysilyl group and/or a cyclicdialkoxysilyl group, (v) silane dimer possessing a mercaptosilane unitthe silicon atom of which is bonded to the silicon atom of a hydrocarbyland/or heterocarbyl silane unit through a bridging dialkoxy group, eachsilane unit optionally possessing at least one hydroxyalkoxysilyl groupand/or a cyclic dialkoxysilyl group, (vi) mercaptosilane oligomer inwhich the silicon atoms of adjacent mercaptosilane units are bonded toeach other through a bridging dialkoxy group, the terminalmercaptosilane units possessing at least one hydroxyalkoxysilyl groupand/or a cyclic dialkoxysilyl group, (vii) hydrocarbyl and/orheterocarbyl silane oligomer in which the silicon atoms of adjacenthydrocarbyl and/or heterocarbyl silane units are bonded to each otherthrough a bridging dialkoxy group, the terminal mercaptosilane unitspossessing at least one hydroxyalkoxysilyl group and/or a cyclicdialkoxysilyl group, and (viii) silane oligomer possessing at least onemercaptosilane unit and at least one hydrocarbyl and/or heterocarbylsilane unit, the silicon atoms of adjacent silane units being bonded toeach other through a bridging dialkoxy group, the terminal silane unitspossessing at least one hydroxyalkoxysilyl group and/or a cyclicdialkoxysilyl group, with the provisio that, where the compositioncontains one or more of (i), (iii) and (vi), the compositionadditionally contains one or more of (ii), (iv), (v), (vii) and (viii),and where the composition contains one or more of (ii), (iv) and (vii),the composition additionally contains one or more of (i), (iii), (v),(vi) and (viii).
 2. The rubber composition of claim 1 wherein rubbercomponent (a) is an organic polymer selected from the group consistingof at least one diene based elastomer or rubber.
 3. The rubbercomposition of claim 1 wherein rubber component (a) is made frommonomers selected from the group consisting of conjugated dienes, vinylaromatic compounds and combinations thereof.
 4. The rubber compositionof claim 1 wherein rubber component (a) is a sulfur curable rubber.
 5. Aprocess for preparing a rubber composition comprising adding to a rubbercomposition reaction-forming mixture in an effective amount of at leastone mercaptofunctional silane composition of claim
 1. 6. The process ofclaim 5 wherein rubber composition reaction forming mixture furthercomprises at least one filler.
 7. The process of claim 5 wherein rubbercomposition reaction-forming mixture further comprises a rubbercomponent.
 8. The process of claim 7 wherein the rubber component is anorganic polymer selected from the group of at least one diene basedelastomer or rubber.
 9. The process of claim 7 wherein the rubbercomponent is made from monomers selected from the group consisting ofconjugated dienes, vinyl aromatic compounds and combinations thereof.10. The process of claim 7 wherein rubber component is a sulfur curablerubber.
 11. The rubber composition of claim 1 wherein at least onemercaptofunctional silane composition is at least one selected from thegroup consisting of structures (10) and (11):[G¹-(SiX^(α) _(u)Z^(β) ^(v)Z^(θ) _(w))_(s)]_(m)[(HS)_(r)-G²-(SiX^(α)_(u)Z^(β) _(v)Z^(θ) _(w))_(s)]_(n)  (10)[[G³-(YG²)_(k)Y]_(j)G²-(SiX^(α) _(u)Z^(β) _(v)Z^(θ)_(w))_(s)]_(m)[(HS)_(r)-G²-(SiX^(α) _(u)Z^(β) _(v)Z^(θ)_(w))_(s)]_(n)  (11) wherein: each occurrence of Y is independentlyselected from a polyvalent species (-Q)_(a)[C(=E)]_(b)(A-)_(c), whereinthe atom (E) is attached to an unsaturated carbon atom; each occurrenceof G¹ is independently selected from the group consisting of monovalentand polyvalent groups derived by substitution of alkyl, alkenyl, aryl,or aralkyl wherein G¹ can have from 1 to about 30 carbon atoms; eachoccurrence of G² is independently selected from the group consisting ofdivalent or polyvalent group derived by substitution of alkyl, alkenyl,aryl, or aralkyl wherein G² can have from 1 to 30 carbon atoms; eachoccurrence of G³ is independently selected from the group consisting ofmonovalent and polyvalent groups derived by substitution of alkyl,alkenyl, aryl, or aralkyl wherein G³ can have from 1 to about 30 carbonatoms, with the proviso that if G³ is monovalent, G³ can be hydrogen;each occurrence of X^(α) is independently selected from the groupconsisting of —Cl, —Br, RO—, RC(═O)O—, R₂C═NO—, R₂NO—, R₂N—, —R,(HO)_(d-1)G⁴O—, HO(CR⁰ ₂)_(f)O—, and HO(CR⁰ ₂CR⁰ ₂O)_(e)— wherein each Ris independently selected from the group consisting of hydrogen,straight, cyclic or branched alkyl that can or can not containunsaturation, alkenyl groups, aryl groups, and aralkyl groups, whereineach R, other than hydrogen, contains from 1 to 18 carbon atoms, G⁴ isindependently a substituted hydrocarbon group of from about 2 to about15 carbon atoms or a substituted heterocarbon group of from about 4 to15 carbon atoms and contains one or more etheric oxygen atoms, R⁰ isindependently given by one of the members listed for R, f is from about2 to about 15, and e is from about 2 to about 7; each occurrence of Q isindependently selected from the group consisting of oxygen, sulfur, and(—NR—) and with the proviso that when Q is sulfur, b is 0; eachoccurrence of A is independently selected from the group consisting ofoxygen, sulfur, and (—NR—) and with the proviso that when A is sulfur, bis 0; each occurrence of E is independently selected from the groupconsisting of oxygen, sulfur, and (—NR—); each occurrence of Z^(β),which forms a bridging structure between two silicon atoms, isindependently selected from the group consisting of,[—OG⁴(OH)_(d-2)O—]_(0.5), [—O(CR⁰ ₂CR⁰ ₂O)_(e)—]_(0.5) and[—O(R⁰CR⁰)_(f)O—]_(0.5), wherein each occurrence of R⁰ is independentlygiven by one of the members listed above for R; and, each occurrence ofG⁴ is independently selected form the group consisting of a substitutedhydrocarbon group from 2 to 15 carbon atoms or a substituted hetercarbonfrom 4 to 15 carbon atoms and contain one or more etheric oxygen atoms;each occurrence of Z^(θ), which forms a cyclic structure with a siliconatom, is independently given by —OG⁴(OH)_(d-2)O—, —O(CR⁰ ₂CR⁰ ₂O)_(f)—and —O(R⁰CR⁰)_(f)O— wherein each occurrence of R⁰ is independently givenby one of the members listed above for R; each occurrence of thesubscripts, a, b, c, d, e, f, j, k, m, n, r, s, u, v, and w are integersindependently given by a is 0 or 1; b is 0 or 1; c is 0 or 1; d is fromabout 2 to about 8; e is from about 2 to about 7; f is from about 2 toabout 15; j is from 1 to about 3; k is from 0 to about 15; m is fromabout 1 to about 20; n is from about 1 to about 20; r is from 1 to about3; and s is from 1 to about 3; u is from 0 to 3; v is from 0 to 3; w isfrom 0 to about 1; with the proviso that u+v+2w=3; and with the provisothat the each of the above structures (10) and/or (11) contains at leastone hydrolysable group, Z^(β) or Z^(θ).
 12. The rubber composition ofclaim 11 wherein rubber component (a) is an organic polymer selectedfrom the group of at least one diene based elastomer or rubber.
 13. Therubber composition of claim 11 wherein rubber component (a) is made frommonomers selected from the group consisting of conjugated dienes, vinylaromatic compounds and combinations thereof.
 14. The rubber compositionof claim 11 wherein rubber component (a) is a sulfur curable rubber. 15.The rubber composition of claim 1 wherein mercaptofunctional silane (a)is selected from the group consisting of3-{4-methyl-2-[2-(4-methyl-2-pentyl-[1,3,2]dioxasilolan-2-yloxy)-propoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol;3-{2-[2-(2-methyl-[1,3,2]dioxasilolan-2-yloxy)-ethoxy]-[1,3,2]dioxasilolan-2-yl}-propane-1-thiol;mixture of3-[2-(3-mercapto-propyl)-[1,3,2]dioxasilinan-2-yloxy]-propan-1-ol and3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propan-1-ol;4-{2-[3-(2-butyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-[1,3,2]dioxasilinan-2-yl}-butane-1-thiol;4-[2-(3-{2-[3-(2-methoxy-ethoxy)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol;4-[5-methyl-2-(2-methyl-3-{5-methyl-2-[3-(2-methylamino-ethylamino)-propyl]-[1,3,2]dioxasilinan-2-yloxy}-propoxy)-[1,3,2]dioxasilinan-2-yl]-butane-1-thiol;2-acetylamino-N-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-acetamide;(2-{3-[3-(2-{3-[2-(4-mercapto-butyl)-5-methyl-[1,3,2]dioxasilinan-2-yloxy]-2-methyl-propoxy}-5-methyl-[1,3,2]dioxasilinan-2-yl)-propyl]-ureido}-ethyl)-urea;4-acetoxy-butyric acid3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propylester; carbonic acid2-[3-(2-{3-[2-(4-mercapto-butyl)-5,5-dimethyl-[1,3,2]dioxasilinan-2-yloxy]-2,2-dimethyl-propoxy}-5,5-dimethyl-[1,3,2]dioxasilinan-2-yl)-propoxycarbonyloxy]-ethylester methyl ester;4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-dimethyl-silanyl}-butane-1-thiol;4-{[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-diethoxy-silanyl}-butane-1-thiol;4-[butyl-[3-(2-dodecyl-4,4,6-trimethyl-[1,3,2]dioxasilinan-2-yloxy)-1,1-dimethyl-butoxy]-(4-mercapto-butyl)-silanyloxy]-2-methyl-pentan-2-ol;4-{(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyl}-2-methyl-butan-1-ol;3-{(3-hydroxy-2-methyl-propoxy)-(4-mercapto-butyl)-[2-methyl-3-(5-methyl-2-octyl-[1,3,2]dioxasilinan-2-yloxy)-propoxy]-silanyloxy}-2-methyl-propan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyl]-2-methyl-butan-1-ol;3-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(4-mercapto-butyl)-silanyloxy]-2-methyl-propan-1-ol;3-[{3-[(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-methyl-octyl-silanyloxy]-3-methyl-butyl}-(3-mercapto-propyl)-silanyloxy]-2-methyl-propoxy}-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propan-1-ol;4-((3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-octyl-silanyl)-2-methyl-butan-1-ol;3-((3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-octyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-octyl-silanyl)-2-methyl-propan-1-ol;4-(benzyl-(3-hydroxy-2-methyl-propoxy)-{4-[(3-hydroxy-2-methyl-propoxy)-{3-[(3-hydroxy-2-methyl-propoxy)-(3-hydroxy-2-methyl-propyl)-phenethyl-silanyloxy]-2-methyl-propoxy}-(3-mercapto-propyl)-silanyl]-2-methyl-butoxy}-silanyl)-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-pent-4-enyl-silanyl]-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-phenethyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol;4-[(3-hydroxy-2-methyl-propoxy)-(4-{(3-hydroxy-2-methyl-propoxy)-(3-mercapto-propyl)-[2-methyl-3-(4-methyl-2-octyl-[1,2]oxasilolan-2-yloxy)-propoxy]-silanyl}-2-methyl-butoxy)-(3-mercapto-propyl)-silanyl]-2-methyl-butan-1-ol;and combinations thereof.
 16. An article of which at least one componentis the cured rubber composition of claim
 1. 17. An article of which atleast one component is the cured rubber composition of claim
 11. 18. Atire at least one component of which comprises the cured rubbercomposition of claim
 1. 19. The tire of claim 18 wherein rubbercomponent (a) is an organic polymer selected from the group of at leastone diene based elastomer or rubber.
 20. The tire of claim 18 whereinrubber component (a) is made from monomers selected from the groupconsisting of conjugated dienes, vinyl aromatic compounds andcombinations thereof.
 21. The tire of claim 18 wherein rubber component(a) is a sulfur curable rubber.
 22. A tire at least one component ofwhich comprises the cured rubber composition of claim
 11. 23. The tireof claim 22 wherein rubber component (a) is an organic polymer selectedfrom the group of at least one diene based elastomer or rubber.
 24. Thetire of claim 22 wherein rubber component (a) is made from monomersselected from the group consisting of conjugated dienes, vinyl aromaticcompounds and combinations thereof.
 25. The tire of claim 22 whereinrubber component (a) is a sulfur curable rubber.